Silanol condensation catalysts for the cross-linking of filled and unfilled polymer compounds

ABSTRACT

The invention relates to a composition of an organofunctional silane compound, particularly of a mono-unsaturated silane compound, and of an organic acid or a precursor compound which releases said organic acid, and to a method for the production of polymer compounds such as granulates and/or finished products from thermoplastic base polymers and/or monomers and/or prepolymers of the thermoplastic base polymer utilizing the composition, the organic acid, or the precursor compound which releases said organic acid. The invention also relates to the produced polymers, filled plastics such as, for example, granulates, finished products, molded bodies and/or articles such as pipes or cables. In addition, the invention relates to a kit containing the composition.

The invention relates to a composition of an organofunctional silanecompound, in particular of a monounsaturated silane compound, and of anorganic acid, or of a precursor compound that liberates an acid, and inparticular relates to an olefinic silicon-containing precursor compoundof an organic acid, and also to processes for producing compoundedpolymer materials, such as granules and/or finished products, made ofthermoplastic parent polymers, and/or monomers, and/or prepolymer of thethermoplastic parent polymers, with use of the composition, of theorganic acid, or of the precursor compound that liberates said acid. Theinvention further relates to the polymers produced, to filled plastics,for example in the form of granules, finished product, moldings, and/oritems such as pipes or cables. A kit comprising the composition is alsodisclosed.

It is known that filled and unfilled compounded polymer materials, inparticular polyethylene (PE) and copolymers thereof, can be produced byusing organotin compounds or aromatic sulfonic acids (Borealis) Ambicat®as silanol condensation catalysts for the crosslinking of silane-graftedor silane-copolymerized polyethylenes. A disadvantage of the organotincompounds is their significant toxicity, while the sulfonic acids arenotable for their pungent odor, which continues through all stages ofthe process into the final product. The compounded polymer materialscrosslinked by sulfonic acids are generally not suitable for use in thefood-and-drinks sector or in the drinking-water-supply sector, forexample for production of drinking-water pipes, because of reactionbyproducts. Dibutyltin dilaurate (DBTDL) and dioctyltin dilaurate (DOTL)are conventional tin-based silanol condensation catalysts, and act ascatalyst by way of their coordination sphere.

It is known that moisture-crosslinkable polymers can be produced bygrafting silanes onto polymer chains in the presence of free-radicalgenerators, where moisture-crosslinking is carried out in the presenceof the abovementioned silane hydrolysis catalysts and/or silanolcondensation catalysts, after the shaping process. Moisture-crosslinkingof polymers using hydrolyzable unsaturated silanes is practicedworldwide for the production of cables, pipes, foams, etc. Processes ofthis type are known as the sioplas process (DE 19 63 571 C3, DE 21 51270 C3, U.S. Pat. No. 3,646,155) and the monosil process (DE 25 54 525C3, U.S. Pat. No. 4,117,195). Whereas the monosil process adds thecrosslinking catalyst before the first step of processing is complete,the sioplas process delays addition of the crosslinking catalyst to thesubsequent step. Another possibility is to copolymerize vinyl-functionalsilanes together with the monomers and/or prepolymers directly to givethe parent polymer, or to couple these subsequently by way of graftingonto the polymer chains.

EP 207 627 discloses further tin-containing catalyst systems and, withthese, modified copolymers based on the reaction of dibutyltin oxidewith ethylene-acrylic acid copolymers. JP 58013613 uses Sn(acetyl)₂ ascatalyst, and JP 05162237 teaches the use of carboxylates of tin, ofzinc, or of cobalt together with hydrocarbon groups as silanolcondensation catalysts, e.g. dioctyltin maleate, monobutyltin oxide,dimethyloxybutyltin, or dibutyltin diacetate. JP 3656545 uses zinc andaluminum soaps for crosslinking, examples being zinc octylate andaluminum laurate. JP 1042509 likewise discloses the use of organic tincompounds for the crosslinking of silanes, but also discloses alkyltitanic esters based on titanium chelate compounds. JP09-040713discloses the production of silane-modified polyolefins by reacting apolyolefin and two modified silane compounds with use of an organic acidas silanol condensation catalyst.

It is an object of the present invention to develop novel silanehydrolysis catalysts and/or silanol condensation catalysts which do nothave the above-mentioned disadvantages of the known catalysts from theprior art, and which can preferably undergo a homogenization process ordispersion process with silane-grafted, and/or silane-copolymerizedpolymers, and/or monomers, or prepolymers. It is preferable that thesilane hydrolysis catalysts and/or silanol condensation catalysts arewaxy to solid, and/or have been applied to a carrier material.

The object is achieved via the composition of the invention,corresponding to the features of claim 1, the masterkit as claimed inclaim 9, and the processes of the invention with the features of claims10 and 11, and also by using the products of the invention, e.g.polymers, compounded polymer materials, products, and the polymer kitcorresponding to the features of claims 13, 14, and 15, and also by theuse as claimed in claim 16. Preferred embodiments can be found in thedependent claims and in the description.

Surprisingly, it has been found that the composition which comprises atleast one hydrolyzable precursor compound of an organic acid, and also,if appropriate, an organofunctional silane compound, can be reacted in asimple and cost-effective manner with thermoplastic parent polymers,monomers, and/or prepolymers of the parent polymers, to give compoundedpolymer materials, and does not have the abovementioned disadvantages,such as toxicity and odor impairment. Another factor, dependent on thecomposition, is that there is then overall no liberation of alcohols inthe process for producing compounded polymer materials.

By way of example, when at least one silicon-containing precursorcompound of an organic acid, for example of the general formula I, wherez=1, 2, or 3, and/or II, where y=0, 1, 2, or 3, and/or where z=0, andOR¹ corresponds to an unsaturated carboxylate moiety, is grafted onto aparent polymer, or is copolymerized with a monomer and/or prepolymer ofthe parent polymer, if appropriate in the presence of a free-radicalgenerator, or is mixed with a corresponding carboxy-substitutedsilane-grafted parent polymer and, if appropriate, after the shapingprocess a crosslinking process takes place in the presence of moisture.The grafting process or copolymerization process can also take place inthe presence of an organofunctional silane compound, an example being anunsaturated alkoxysilane of the general formula III.

The invention therefore provides a composition which comprises, ascomponents of group a), at least one silicon-containing precursorcompound of an organic acid, and/or one organofunctional silane compoundand, if appropriate, as components of group b), one organic acid, andone silicon-free precursor compound containing an organic acid, anexample being an alkali-metal or, respectively, alkaline-earth-metalsalt of an organic acid, sodium myristate, magnesium dimyristate, sodiumlaurate, magnesium laurate, sodium stearate, magnesium distearate; or ananhydride or ester, examples being the triglycerides that occur in fatsand in oils.

Particularly preferred compositions comprise, as components, at leastone organofunctional silane compound and, selected from the group of theacids or precursor compounds of the acids, at least onesilicon-containing precursor compound of an organic acid, and/or oneorganic acid, and/or one silicon-free precursor compound containingorganic acid. By way of example, said preferred composition can comprisean unsaturated alkoxysilane of the general formula III, an example beingvinylalkoxysilane, and a compound of the general formula I and/or II,and/or one of the fatty acids mentioned hereinafter.

Alternative preferred compositions comprise, from the group of the acidsor precursor compounds of the acids, at least one silicon-containingprecursor compound of an organic acid, and/or one organic acid, and/orone silicon-free precursor compound at least two of the compoundsmentioned, i.e. of the precursor compounds or acid and, if appropriate,at least one organofunctional silane compound.

One example of these types of compositions is a silicon-containingprecursor compound of an organic acid, an example being acarboxy-substituted silane, e.g. vinyltristearylsilane and, as secondcompound, an organic acid, such as myristic acid or oleic acid. Anotherexample is a composition comprising a tetracarboxy-substituted silane,such as tetramyristylsilane, tetralaurylsilane, tetracaprinylsilane, orcorresponding mixed silanes, or a mixture of the silanes with myristicacid, capric acid, lauric acid, and/or else behenic acid.

Compositions of the invention are suitable for use in a monosil processor sioplas process with thermoplastic parent polymers, or in acopolymerization process with monomers and/or prepolymers ofthermoplastic parent polymers.

Thermoplastic parent polymers for the purposes of the invention are inparticular acrylonitrile-butadiene-styrene (ABS), polyamides (PA),polymethyl methacrylate (PMMA), polycarbonate (PC), polyethylene (PE),polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), and alsoethylene-vinyl acetate copolymers (EVA), EPDM, or EPM, which arepolymers based on ethylene units, and/or celluloid, orsilane-copolymerized polymers, and monomers and/or prepolymers areprecursor compounds of said parent polymers, examples being ethylene andpropylene. Other thermoplastic parent polymers are mentioned below.

In particular, the composition is in essence anhydrous, in order tosuppress any undesired hydrolysis and/or condensation prior to theactual use in the monosil process or sioplas process, or cocondensationprocess.

The composition comprises, as component of group a), at least one

i) silicon-containing precursor compound of an organic acid of thegeneral formula I and/or II, and/or

ii) an organofunctional silane compound which corresponds to anunsaturated alkoxysilane,

where i) corresponds to the general formula I and/or II

(A)_(z)SiR² _(x)(OR¹)_(4-z-x)   (I)

(R¹O)_(3-y-u)(R²)_(u)(A)_(y)Si-A-Si(A)_(y)(R²)_(u)(OR¹)_(3-y-u)   (II)

-   -   where, mutually independently, z is 0, 1, 2, or 3, x is 0, 1, 2,        or 3, y is 0, 1, 2, or 3, and u is 0, 1, 2, or 3, with the        proviso that in formula I z+x is smaller than or equal to 3, and        in formula II y+u is independently smaller than or equal to 2,        and preference is given to the tricarboxysilanes of the formula        I where z=1, x=0 or, z=0 and x=1, and/or tetracarboxysilanes        where z=0 and x=0, are suitable, as also are the        dicarboxysilanes, where z=1 and x=1,    -   where A is mutually independently in formula I and/or II a        monovalent olefin group, particular examples being        -   (R⁹)₂C═C(R⁹)-M_(k)-, in which R⁹ are identical or different,            and R⁹ is a hydrogen atom or a methyl group or a phenyl            group, the group M is a group from —CH₂—, —(CH₂)₂—,            —(CH₂)₃—, —O(O)C(CH₂)₃—, or —C(O)O—(CH₂)₃—, k is 0 or 1,            examples being vinyl, allyl, 3-methacryloxypropyl, and/or            acryloxypropyl, n-3-pentenyl, n-4-butenyl, or        -   isoprenyl, 3-pentenyl, hexenyl, cyclohexenyl, terpenyl,            squalanyl, squalenyl, polyterpenyl, betulaprenoxy,            cis/trans-polyisoprenyl, or        -   R⁸—F_(g)—[C(R⁸)═C(R⁸)—C(R⁸)═C(R⁸)]_(r)—F_(g)—, in which R⁸            are identical or different, and R⁶ is a hydrogen atom or an            alkyl group having from 1 to 3 carbon atoms, or an aryl            group, or an aralkyl group, preferably a methyl group or a            phenyl group, groups F are identical or different, and F is            a group from —CH₂—, —(CH₂)₂—, —(CH₂)₃—, —O(O)C(CH₂)₃—, or            —C(O)O—(CH₂)₃—, r is from 1 to 100, in particular 1 or 2,            and g is 0 or 1,        -   and where A takes the form of a divalent olefin moiety in            formula II, examples being the corresponding alkenylenes,            such as 2-pentenylene, 1,3-butadienylene, iso-3-butenylene,            pentenylene, hexenylene, hexenedienylene, cyclohexenylene,            terpenylene, squalanylene, squalenylene, polyterpenylene,            cis/trans-polyisoprenylene,        -   R¹ in formula I and/or II corresponds mutually independently            to a carbonyl-R³ group, i.e. a —(CO)R³ group (—(C═O)—R³), so            that —OR¹ is —O(CO)R³, where R³ corresponds to a hydrocarbon            moiety having from 1 to 45 carbon atoms, in particular to an            unsubstituted or substituted hydrocarbon moiety (HC moiety)            having from 4 to 45 carbon atoms, in particular having from            6 to 45 carbon atoms, preferably having from 6 to 22 carbon            atoms, particularly preferably having from 6 to 14 carbon            atoms, with preference having from 8 to 13 carbon atoms, and            in particular to a linear, branched, and/or cyclic            unsubstituted and/or substituted hydrocarbon moiety, and            particularly preferably to a hydrocarbon moiety of a natural            or synthetic fatty acid, and in particular R³ in R¹ is,            mutually independently, a saturated HC moiety using            —C_(n)H_(2n+1), where n=4 to 45, examples being —C₄H₉,            —C₅H₁₁, —C₆H₁₃, —C₇H₁₅, —C₈H₁₇, —C₉H₁₉, —C₁₀H₂₁, —C₁₁H₂₃,            —C₁₂H₂₅, —C₁₃H₂₇, —C₁₄H₂₉, —C₁₅H₃₁, —C₁₆H₃₃, —C₁₇H₃₅,            —C₁₈H₃₇, —C₁₉H₃₉, —C₂₀H₄₁, —C₂₁H₄₃, —C₂₂H₄₅, —C₂₃H₄₇,            —C₂₄H₄₉, —C₂₅H₅₁, —C₂₆H₅₃, —C₂₇H₅₅, —C₂₈H₅₇, —C₂₉H₅₉, or            else preferably an unsaturated HC moiety, examples being            —C₁₀H₁₉, —C₁₅H₂₉, —C₁₇H₃₃, —C₁₇H₃₂, —C₁₉H₃₇, —C₂₁H₄₁,            —C₂₁H₄₁, —C₂₁H₄₁, —C₂₃H₄₅, —C₁₇H₃₁, —C₁₇H₂₉, —C₁₇H₂₉,            —C₁₉H₃₁, —C₁₉H₂₉, —C₂₁H₃₃ and/or —C₂₁H₃₁. The composition            can likewise use the relatively short-chain HC moieties R³,            examples being —C₄H₉, —C₃H₇, —C₂H₅, —CH₃ (acetyl) and/or            R³═H (formyl). However, because of the low hydrophobicity of            the HC moieties, the composition is generally based on            compounds of the formula I and/or II in which R¹ is a            carbonyl-R³ group selected from the group of R³ having an            unsubstituted or substituted hydrocarbon moiety having from            4 to 45 carbon atoms, in particular having from 6 to 22            carbon atoms, preferably having from 8 to 22 carbon atoms,            particularly preferably having from 6 to 14 carbon atoms, or            with preference having from 8 to 13 carbon atoms.

R² is mutually independently a hydrocarbon group, in particular asubstituted or unsubstituted linear, branched, and/or cyclic alkyl,alkenyl, alkylaryl, alkenylaryl, and/or aryl group having from 1 to 24carbon atoms, preferably having from 1 to 18 carbon atoms, and inparticular having from 1 to 3 carbon atoms in the case of alkyl groups.Particularly suitable alkyl groups are ethyl groups, n-propyl groups,and/or isopropyl groups. Suitable substituted hydrocarbons are inparticular halogenated hydrocarbons, examples being 3-halopropyl, suchas 3-chloropropyl or 3-bromopropyl groups, where these are, ifappropriate, accessible to nucleophilic substitution or else improveprocessability.

It is therefore preferably also possible to use silicon-containingprecursor compounds of an organic acid of the general formula I and/orII which correspond to alkyl-substituted di- or tricarboxysilanes wherez=0 and x=1 or 2. Examples here are methyl-, dimethyl-, ethyl-, ormethylethyl-substituted carboxysilanes based on capric acid, myristicacid, oleic acid, or lauric acid.

Carbonyl-R³ groups are the acid moieties of the organic carboxylicacids, an example being R³—(CO)—, where these in the form of carboxygroups in accordance with the formulae have bonding to the siliconSi—OR¹, as set out above. The acid moieties of the formula I and/or IIcan generally be obtained from naturally occurring or synthetic fattyacids, examples being the saturated fatty acids valeric acid (pentanoicacid, R³═C₄H₉), caproic acid (hexanoic acid, R³═C₅H₁₁), enanthic acid(heptanoic acid, R³═C₆H₁₃), caprylic acid (octanoic acid, R³═C₇H₁₅),pelargonic acid (nonanoic acid, R³═C₈H₁₇), capric acid (decanoic acid,R³=C₉H₁₉), lauric acid (dodecanoic acid, R³═C₉H₁₉), undecanoic acid(R³═C₁₀H₂₃), tridecanoic acid (R³═C₁₂H₂₅), myristic acid (tetradecanoicacid, R³═C₁₃H₂₇), pentadecanoic acid (R³═C₁₄H₂₉), palmitic acid(hexadecanoic acid, R³═C₁₅H₃₁), margaric acid (heptadecanoic acid,R³═C₁₆H₃₃), stearic acid (octadecanoic acid, R³═C₁₇H₃₅) nonadecanoicacid (R³═C₁₈H₃₇), arachic acid (eicosanoic/icosanoic acid, R³═C₁₉H₃₉),behenic acid (docosanoic acid, R³═C₂₁H₄₃) lignoceric acid (tetracosanoicacid, R³═C₂₃H₄₇), cerotinic acid (hexacosanoic acid, R³═C₂₅H₅₁),montanic acid (octacosanoic acid, R³═C₂₇H₅₅), and/or melissic acid(triacontanoic acid, R³═C₂₉H₅₉), and also the short-chain unsaturatedfatty acids, such as valeric acid (pentanoic acid, R³═C₄H₉), butyricacid (butanoic acid, R³═C₃H₇), propionic acid (propanoic acid, R³═C₂H₅),acetic acid (R³═CH₃), and/or formic acid (R³═H), and can be used assilicon-containing precursor compound of the formula I and/or II of theotherwise purely organic silanol condensation catalysts.

It is however preferable, in the formula I and/or II, to use fatty acidshaving a hydrophobic HC moiety, where these are sufficientlyhydrophobic, do not exhibit any unpleasant odor after liberation, and donot exude from the polymers produced. By way of example, said exudationrestricts the possible use of relatively high concentrations of stearicacid and palmitic acid. By way of example, at a concentration above avalue as low as about 0.01% by weight of the liberated stearic acid orpalmitic acid, based on the overall constitution of the polymer, a waxyexudation is observed on the polymers produced. Preferred acids in theformulae I and/or II are therefore capric acid, lauric acid, andmyristic acid, but behenic acid can also be used with advantage.

The naturally occurring or synthetic unsaturated fatty acids cansimilarly preferably be converted to the precursor compounds of theformula I and/or II. They can simultaneously perform two functions,firstly serving as silanol condensation catalyst, and, by virtue oftheir unsaturated hydrocarbon moieties, participating directly in thefree-radical polymerization reaction. Preferred unsaturated fatty acidsare sorbic acid (R³═C₅H₇), undecylenic acid (R³═C₁₀H₁₉), palmitoleicacid (R³═C₁₅H₂₉), oleic acid (R³═C₁₇H₃₃), elaidic acid (R³═C₁₇H₃₃),vaccenic acid (R³═C₁₉H₃₇), icosenoic acid (R³═C₂₁H₄₁), cetoleic acid(R³═C₂₁H₄₁), erucic acid (R³═C₂₁H₄₁), nervonic acid (R³═C₂₃H₄₅),linoleic acid (R³═C₁₇H₃₁), alpha-linolenic acid (R³═C₁₇H₂₉),gamma-linolenic acid (R³═C₁₇H₂₉), arachidonic acid (R³═C₁₉H₃₁),timnodonic acid (R³═C₁₉H₂₉), clupanodonic acid (R³═C₂₁H₃₃), ricinoleicacid (12-hydroxy-9-octadecenoic acid (R³═C₁₇H₃₃), and/or cervonic acid(R³═C₂₁H₃₁).

Other advantageous acids from which the precursor compounds of theformula I and/or II having R³—COO or R¹O can be produced are glutaricacid, lactic acid (R¹ being (CH₃)(HO)CH—), citric acid (R¹ beingHOOCCH₂C(COOH)(OH)CH₂—), vulpinic acid, terephthalic acid, gluconicacid, and adipic acid, where it is also possible that all of the carboxygroups have been Si-functionalized, benzoic acid (R¹ being phenyl),nicotinic acid (vitamin B3, B5). However, it is also possible to use thenatural or synthetic amino acids, in such a way that R¹ corresponds toappropriate moieties such as those deriving from tryptophan, L-arginine,L-histidine, L-phenylalanine, or L-leucine, where L-leucine can be usedwith preference. It is also correspondingly possible to use thecorresponding D-amino acids or a mixture of L- and D-amino acids, or anacid such as D[(CH₂)_(d))COOH]₃, where D=N, P, and d is from 1 to 12,preferably 1, 2, 3, 4, 5, or 6, where the hydroxy group of eachcarboxylic acid function can independently have been Si-functionalized.

The composition can therefore also comprise corresponding compounds ofthe formula I and/or II based on moieties of said acids.

The silicon-containing precursor compound of an organic acid is inparticular active in hydrolyzed form as silane hydrolysis catalystand/or silane condensation catalyst, and is also itself suitable inhydrolyzed or nonhydrolyzed form for grafting on a polymer and/orcopolymerization with a parent polymer, polymer/monomer, or prepolymer.In hydrolyzed form, the silanol compound formed contributes tocrosslinking by means of resultant Si—O—Si siloxane bridges during thecondensation reaction. Said crosslinking can use other silanols,siloxanes, or can generally use functional groups which are present onsubstrates, on fillers, and/or on carrier materials and which aresuitable for the crosslinking reaction. Preferred fillers and/or carriermaterials are therefore aluminum hydroxides, magnesium hydroxides, fumedsilica, precipitated silica, silicates, and also other fillers andcarrier materials mentioned below.

Very particularly preferably the inventive composition comprises, ascomponent (i) in group a), vinylsilane trimyristate, vinylsilanetrilaurate, vinylsilane tricaprate, or else corresponding allylsilanecompounds of the abovementioned acids, and/or silane tetracarboxylatesSi(OR¹)₄, examples being silane tetramyristate, silane tetralaurate, andsilane tetra-caprate, and it can also be advantageous to add a certainamount of vinylsilane tristearate, vinylsilane tripalmitate, allylsilanetristearate, and/or allylsilane tripalmitate. The amounts used of silanestearates and/or silane palmitates should preferably be such that nomore than 1.0% by weight, preferably from 0.001% by weight to 0.8% byweight, in particular from 0.01% to 0.6% by weight, of liberated acid,such as stearic acid or palmitic acid, is present in the overallconstitution in % by weight of the resultant compounded polymer materialor polymer. A corresponding limit also applies when adding free stearicand/or palmitic acid.

Particular preference is always given to those compounds of group a)and/or b) in which the organic acid has at least one hydrophobic groupwhich permits solvation or dispersibility in respect of the plastic.These are in particular long-chain, branched or cyclic, nonpolar, inparticular unsubstituted hydrocarbon moieties, in particular having from6 to 22 carbon atoms, preferably having from 8 to 14 carbon atoms,particularly preferably having from 8 to 13 carbon atoms, having atleast one carboxylic acid group. Preferred substituted hydrocarbonmoieties that can be used are halogen-substituted HC moieties.

As indicated above, the composition comprises, as component of group a),at least one i) silicon-containing precursor compound of an organic acidof the general formula I and/or II, and/or

ii) one organofunctional silane compound which corresponds to anunsaturated or olefinic alkoxysilane, where the silane compound ii)particularly preferably corresponds to a monounsaturated alkoxysilane.

For the purposes of the present invention, the organofunctional silanecompound is particularly suitable for grafting on a polymer and/or forcopolymerization with a monomer, prepolymer, or parent polymer, andsubsequent moisture-crosslinking. For the purposes of the presentinvention, it is preferable that the silicon-containing precursorcompound I and/or II is also suitable for grafting on a polymer and/orcopolymerization with a monomer, prepolymer, or parent polymer, andsubsequent moisture-crosslinking.

The production of the carboxysilanes has long been known to the personskilled in the art. By way of example, U.S. Pat. No. 4,028,391 disclosesprocesses for their production in which chlorosilanes are reacted withfatty acids in pentane. U.S. Pat. No. 2,537,073 discloses anotherprocess. The acid can, for example, be heated directly in a nonpolarsolvent, such as pentane, with trichlorosilane or with a functionalizedtrichlorosilane, at reflux, to give the carboxysilane. In an example forproduction of tetracarboxysilanes, tetrachlorosilane is reacted with thecorresponding acid in a suitable solvent (Zeitschrift für Chemie (1963),3(12), 475-6). Other processes relate to the reaction of the salts oranhydrates of the acids with tetrachlorosilane or with functionalizedtrichlorosilanes.

As organofunctional silane compound ii) of group a) it is in particularpossible to use a compound corresponding to the general formula III,

(B)_(b)SiR⁴ _(a)(OR⁵)_(3-b-a)   (III)

-   -   where, mutually independently, b is 0, 1, 2, or 3, and a is 0,        1, 2, or 3, with the proviso that in formula III a +b is smaller        than or equal to 3,    -   where B, mutually independently, is a monovalent        (R⁷)₂C═C(R⁷)-E_(q)- group in formula III, in which R⁷ are        identical or different, and R⁷ is a hydrogen atom or a methyl        group or a phenyl group, the group E is a group from —CH₂—,        —(CH₂)₂—, —(CH₂)₃—, —O(O)C(CH₂)₃—, or —C(O)O—(CH₂)₃—, q is 0 or        1, examples being vinyl, allyl, n-3-pentyl, n-4-butenyl,        3-methacryloxypropyl, and/or acryloxypropyl, or isoprenyl,        hexenyl, cyclohexenyl, terpenyl, squalanyl, squalenyl,        polyterpenyl, betulaprenoxy, cis/trans-polyisoprenyl, or B        comprises an olefin group, for example        R⁶-D_(p)-[C(R⁶)═C(R⁶)—C(R⁶)═C(R⁶)]_(t)-D_(p)-, in which R⁶ are        identical or different, and R⁶ is a hydrogen atom or an alkyl        group having from 1 to 3 carbon atoms, or an aryl group, or an        aralkyl group, preferably a methyl group or a phenyl group, the        groups D are identical or different, and D is a group from        —CH₂—, —(CH₂)₂—, —(CH₂)₃—, —O(O)C(CH₂)₃—, or —C(O)O—(CH₂)₃—, and        p is 0 or 1, and t is 1 or 2.    -   R⁵ is, mutually independently, methyl, ethyl, n-propyl, or        isopropyl,    -   R⁴ is, mutually independently, a substituted or unsubstituted        hydrocarbon group, in particular a substituted or unsubstituted        linear, branched, and/or cyclic alkyl, alkenyl, alkylaryl,        alkenylaryl, and/or aryl group having from 1 to 24 carbon atoms,        in particular having from 1 to 16 carbon atoms, preferably        having from 1 to 8 carbon atoms. In particular, the substituted        groups are hydrophobic.    -   A particularly suitable alkyl group is an ethyl, n-propyl,        isopropyl, n-butyl, isobutyl, cyclohexyl, n-octyl, isooctyl, or        hexadecyl group, and a particularly suitable substituted alkyl        group is a haloalkyl group having chlorine substituents or        bromine substituents, preference being given to haloalkyl groups        suitable for nucleophilic substitution, examples being        3-chloropropyl groups or 3-bromopropyl groups.

In particular if the composition has no components of group b), it isparticularly preferable that B comprises at least one olefin group, anexample being polyethylene, polypropylene, propylene copolymer, orethylene copolymer, if appropriate together with a free-radicalgenerator and with other stabilizers and/or additives.

It is very particularly preferable that the inventive compositioncomprises, as component (ii), vinyltrimethoxysilane,vinyltriethoxysilane, vinylmethyldialkoxysilane,vinyltriethoxymethoxysilane (VTMOEO), vinyltriisopropoxysilane,vinyltri-n-butoxysilane, 3-methacryloxypropyltriethoxysilane,3-methacryloxypropyltrimethoxysilane (MEMO), and/orvinylethoxydimethoxysilane, and/or allylalkoxysilanes, such asallyltriethoxysilane, or unsaturated siloxanes, preferred examples beingoligomeric vinylsiloxanes, or a mixture of the abovementioned compounds.Preferred organofunctional silane compounds contain either a vinyl groupor methacrylic group, since these compounds are reactive toward freeradicals and are suitable for grafting onto a polymer chain or forcopolymerization with monomers or with prepolymers.

The form taken by the composition is usually liquid. However, it ispreferable, for greater ease of metering, that the composition isprovided in the form of solid, flowable formulation, for example on acarrier material and/or filler. The carrier can be porous, particulate,swellable or, if appropriate, take the form of a foam. Suitable carriermaterials are in particular polyolefins, such as PE, PP, EVA, or polymerblends, and suitable fillers are in particular inorganic or mineralfillers which can advantageously have reinforcing, extending, or elseflame-retardant effect. The carrier materials and fillers are specifiedin more detail below.

In one preferred embodiment, the composition is composed of a selectioni) of a precursor compound of the formula I and/or II, and/or ii) of amonounsaturated alkoxysilane, and/or of an organic acid, and/or of afree-radical generator and also, if appropriate, of at least onestabilizer and/or additional substance, and/or a mixture of these.

In another preferred embodiment, the composition is composed of aselection i) of a precursor compound of the formula I and/or II, whereR¹ corresponds to a carbonyl-R³ group where R³ is from 4 to 45 carbonatoms, preferably having from 6 to 45 carbon atoms, in particular havingfrom 6 to 22 carbon atoms, preferably having from 8 to 22 carbon atoms,particularly preferably having from 6 to 14 carbon atoms, withparticular preference where R³ is from 8 to 13 carbon atoms, inparticular where R³ is from 11 to 13 carbon atoms, and/or ii) of anolefinic alkoxysilane, and/or of a free-radical generator, and also, ifappropriate, of at least one stabilizer and/or additional substance,and/or a mixture of these.

In alternative preferred embodiments, the composition is composed of aselection i) of a precursor compound of the formula I and/or II, inparticular where R¹ corresponds to a carbonyl-R³ group where R³ is from4 to 45 carbon atoms, preferably having from 6 to 45 carbon atoms, inparticular having from 6 to 22 carbon atoms, preferably having from 8 to22 carbon atoms, particularly preferably having from 6 to 14 carbonatoms, with particular preference where R³ is from 11 to carbon atoms,and/or ii) of an olefinic alkoxysilane, and also, if appropriate, of atleast one stabilizer and/or additional substance, and/or a mixture ofthese.

As at least one organic acid can comprise as components in group b):

-   -   iii.a) a saturated and/or unsaturated fatty acid (naturally        occurring or synthetic)    -   an example being valeric acid, caproic acid, enanthic acid,        caprylic acid, pelargonic acid, capric acid, lauric acid,        undecanoic acid, tridecanoic acid, myristic acid, pentadecanoic        acid, palmitic acid, margaric acid, stearic acid, nonadecanoic        acid, arachic acid, behenic acid, lignoceric acid, cerotinic        acid, montanic acid, melissic acid, valeric acid, butyric acid,        propionic acid, acetic acid, formic acid, undecylenic acid,        palmitoleic acid, oleic acid, elaidic acid, vaccenic acid,        icosenoic acid, cetoleic acid, erucic acid, nervonic acid,        linoleic acid, alpha-linolenic acid, gamma-linolenic acid,        arachidonic acid, timnodonic acid, clupanodonic acid, cervonic        acid, lignoceric acid (H₃C—(CH₂)₂₂—COOH), cerotinic acid, lactic        acid, citric acid, benzoic acid, nicotinic acid, arachidonic        acid (5,8,11,14-eicosatetraenoic acid, C₂₀H₃₂O₂), erucic acid        (cis-13-docosenoic acid, H₃C—(CH₂)₇—CH═CH—(CH₂)₁₁—COOH),        gluconic acid, icosenoic acid (H₃C—(CH₂)₇—CH═CH—(CH₂)₉—COOH),        ricinoleic acid (12-hydroxy-9-octadecenoic acid), sorbic acid        (C₆H₈O₂), and/or naturally occurring or else synthetic amino        acids, such as tryptophan, L-arginine, L-histidine,        L-phenylalanine, or L-leucine, where L-leucine is preferred, a        dicarboxylic acid, such as adipic acid, glutaric acid,        terephthalic acid (benzene-1,4-dicarboxylic acid), where lauric        acid and myristic acid are preferred, or an acid such as        D[(CH₂)_(d))COOH]₃, where D=N, P, and n=1 to 12, preferably 1,        2, 3, 4, 5, or 6,

and/or as

-   -   iii.b) an acid-containing silicon-free precursor compound, an        example being an organic anhydride or an ester, in particular of        the abovementioned acids, or else natural or synthetic        triglycerides and/or phosphoglycerides.

In general terms, the acids having relatively long hydrophobichydrocarbon moieties, beginning with valeric acid, and preferably capricacid, lauric acid, and/or myristic acid, have good suitability assilanol condensation catalyst. The less hydrophobic acids are regardedmerely as useful for the reaction with thermoplastic hydrophobicpolymers, examples being propionic acid, acetic acid, and formic acid.Correspondingly, the fatty acids that have strong odors, for examplebutyric acid and caprylic acid are also only useful or have low to zerosuitability for use in a composition, masterkit, polymer kit, or aprocess of the invention, because of the pungent odor. This isparticularly applicable when the resultant polymers or compoundedpolymer materials are intended for further use in the production ofdrinking-water pipes.

Organic acids are carboxylic acids which have no sulfate groups orsulfonic acid groups, and in particular they are organic acidscorresponding to R³—COOH; the anhydrides, esters, or salts of theseorganic acids can also be regarded as silicon-free precursor compound,and they particularly preferably have a long-chain, nonpolar, inparticular substituted or unsubstituted hydrocarbon moiety, where thehydrocarbon moiety can be saturated or unsaturated, for example where R³is from 1 to 45 carbon atoms, in particular having from 4 to 45 carbonatoms, preferably having from 8 to 45 carbon atoms, in particular havingfrom 6 to 22 carbon atoms, preferably having from 8 to 22 carbon atoms,particularly preferably having from 6 to 14 carbon atoms, withparticular preference where R³ is from 8 to 13 carbon atoms, whereparticular preference is given to R³ being from 11 to 13 carbon atoms;an example of these materials is lauric acid or myristic acid; orhydrogen (R³) and at least one carboxylic acid group (COOH). Materialsexplicitly excluded from the definition of the organic acids are organicarylsulfonic acids, such as sulfophthalic acid, and alsonaphthalenedisulfonic acids.

Marked preference is therefore given to those acids having long-chain,hydrophobic hydrocarbon moieties. These acids can also function asdispersing agents and/or processing aids. In general terms, the acidsthat can be used in the form of organic acids as silanol condensationcatalyst comprise the naturally occurring or synthetic fatty acids,examples being the following saturated fatty acids: valeric acid(pentanoic acid, R³═C₄H₉), caproic acid (hexanoic acid, R³═C₅H₁₁),enanthic acid (heptanoic acid, R³═C₆H₁₃), caprylic acid (octanoic acid,R³═C₇H₁₅), pelargonic acid (nonanoic acid, R³═C₈H₁₇), capric acid(decanoic acid, R³═C₉H₁₉), undecanoic acid (R³═C₁₀H₂₃), tridecanoic acid(R³═C₁₂H₂₅), lauric acid (dodecanoic acid, R³═C₉H₁₉), myristic acid(tetradecanoic acid, R³═C₁₃H₂₇), pentadecanoic acid (R³═C₁₄H₂₉),palmitic acid (hexadecanoic acid, R³═C₁₅H₃₁), margaric acid(heptadecanoic acid, R³═C₁₆ 14 ₃₃), stearic acid (octadecanoic acid,R³═C₁₇H₃₅), nonadecanoic acid (R³═C₁₈H₃₇), arachic acid(eicosanoic/icosanoic acid, R³═C₁₉H₃₉), behenic acid (docosanoic acid,R³═C₂₁14₄₃), lignoceric acid (tetra-cosanoic acid, R³═C₂₃H₄₇), cerotinicacid (hexacosanoic acid, R³═C₂₅H₅₁), montanic acid (octacosanoic acid,R³═C₂₇H₅₅), and/or melissic acid (triacontanoic acid, R³═C₂₉H₅₉), andalso the short-chain unsaturated fatty acids, such as valeric acid(pentanoic acid, R³═C₄H₉), butyric acid (butanoic acid, R³═C₃H₇),propionic acid (propanoic acid, R³═C₂H₅), acetic acid (R³═CH₃), and/orformic acid (R³═H), where the short-chain fatty acids mentioned are notsuitable as dispersing agents and/or processing aids and can thereforebe omitted in preferred compositions. Lauric acid and/or myristic acidare particularly preferred.

Similarly preferred is the use of naturally occurring or syntheticunsaturated fatty acids which can perform two functions, firstly servingas silanol condensation catalyst, and, by virtue of their unsaturatedhydrocarbon moieties, being capable of participating directly in thefree-radical polymerization reaction. Preferred unsaturated fatty acidsare sorbic acid (R³═C₅H₇), undecylenic acid (R³═C₁₀H₁₉), palmitoleicacid (R³═C₁₅H₂₉), oleic acid (R³═C₁₇H₃₃), elaidic acid (R³═C₁₇H₃₃),vaccenic acid (R³═C₁₉H₃₇), icosenoic acid (R³═C₂₁H₄₁;(H₃C—(CH₂)₇—CH═CH—(CH₂)₉—COOH)), cetoleic acid (R³═C₂₁H₄₁), erucic acid(R³═C₂₁H₄₁; cis-13-docosenoic acid, H₃C—(CH₂)₇—CH═CH—(CH₂)₁₁—COOH),nervonic acid (R³═C₂₃H₄₅), linoleic acid (R³═C₁₇H₃₁), alpha-linolenicacid (R³═C₁₇H₂₉), gamma-linolenic acid (R³═C₁₇H₂₉), arachidonic acid(R³═C₁₉H₃₁, 5,8,11,14-eicosatetraenoic acid, C₂₀H₃₂O₂), timnodonic acid(R³═C₁₉H₂₉), clupanodonic acid (R³═C₂₁H₃₃), ricinoleic acid(12-hydroxy-9-octadecenoic acid (R³═C₁₇H₃₃O), and/or cervonic acid(R³═C₂₁H₃₁).

Other advantageous acids are lignoceric acid (H₃C—(CH₂)₂₂—COOH), ceroticacid, lactic acid, citric acid, benzoic acid, nicotinic acid (vitaminB3, B5), gluconic acid or a mixture of the acids. However, it is alsopossible to use the natural or synthetic amino acids, such astryptophan, L-arginine, L-histidine, L-phenylalanine, or L-leucine,where L-leucine is preferred, and it is correspondingly also possible touse the corresponding D-amino acids, or a mixture of the amino acids, ora dicarboxylic acid, such as adipic acid, glutaric acid, terephthalicacid (benzene-1,4-dicarboxylic acid), or else an acid such asD[(CH₂)_(d))COOH]₃, where D=N, and P and n=from 1 to 12, preferably 1,2, 3, 4, 5, or 6. The corresponding anhydrides, esters or salts, forexample alkali-metal salts, alkaline-earth-metal salts, or ammoniumsalts, of these acids can likewise be used.

In general terms it is also possible that the acid-containingsilicon-free precursor compound used comprises esters and/or lactones,in particular of the abovementioned acids or, for example, thetriglycerides that occur in fats or in oils, particular examples beingneutral fats, or else phosphoglycerides, such as lecithin,phosphatidylethanolamine, phosphatidylinositol, phosphatidylserine,and/or diphosphatidylglycerol. It is also possible to use synthetictriglycerides, alongside naturally occurring triglycerides of vegetableorigin and of animal origin.

A general requirement placed upon the precursor compound(silicon-containing and/or silicon-free) is that it is hydrolyzableunder the conditions of the monosil and/or sioplas process, and thusliberates the free organic acid. It is preferable that the onset of thehydrolysis does not precede the crosslinking step of the processes, andthat in particular it occurs after the shaping process, for example withintroduction into the waterbath, or after the shaping process in thepresence of moisture. Compounds excluded from the silicon-free precursorcompounds are advantageously those which when hydrolyzed give aninorganic and an organic acid. An inorganic acid here does not include asilanol. By way of example, the term silicon-free precursor compoundsdoes not cover acyl chlorides or in general terms corresponding acylhalides of the abovementioned organic acids. Nor are organic acidperoxides to be understood as silicon-free precursor compound.

One preferred composition which is particularly suitable for producingcompounded polymer materials comprises, as component c), at least onefree-radical generator. Preferred free-radical generators are organicperoxides and/or organic peresters, or a mixture of these, preferredexamples being tert-butyl peroxypivalate, tert-butyl2-ethylperoxyhexanoate, dicumyl peroxide, di-tert-butyl peroxide,tert-butyl cumyl peroxide, 1,3-di(2-tert-butylperoxyisopropyl)benzene,2,5-dimethyl-2,5-bis(tert-butylperoxy)hex-3-yne, di-tert-amyl peroxide,1,3,5-tris(2-tert-butylperoxyisopropyl)benzene,1-phenyl-1-tert-butylperoxyphthalide,alpha,alpha′-bis(tert-butylperoxy)diisopropylbenzene,2,5-dimethyl-2,5-di-tert-butylperoxyhexane,1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane (TMCH). It can alsobe advantageous to use n-butyl 4,4-di(tert-butylperoxy)valerate, ethyl3,3-di(tert-butylperoxy)butyrate, and/or3,3,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane.

The composition can moreover comprise, as component d), at least onestabilizer and/or other additional substance, and/or a mixture of these.The stabilizer and/or other additional substances used can, ifappropriate, comprise metal deactivators, processing aids, inorganic ororganic pigments, fillers, carrier materials, and adhesion promoters.Examples of these are titanium dioxide (TiO₂), talc, clay, quartz,kaolin, aluminum hydroxide, magnesium hydroxide, bentonite,montmorillonite, mica (muscovite mica), calcium carbonate (chalk,dolomite), dyes, pigments, talc, carbon black, SiO₂, precipitatedsilica, fumed silica, aluminum oxides, such as alpha- and/orgamma-aluminum oxide, aluminum oxide hydroxides, boehmite, baryte,barium sulfate, lime, silicates, aluminates, aluminum silicates, and/orZnO, or a mixture of these. It is preferable that the carrier materialsor additional substances, such as pigments or fillers, are pulverulent,particulate, porous, or swellable or, if appropriate, take the form of afoam.

Examples of preferred metal deactivators areN,N′-bis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propion-yl)hydrazine, andalsotris(2-tert-butyl-4-thio(2′-methyl-4-hydroxy-5′-tert-butyl)phenyl-5-methyl)phenylphosphite.

The composition can moreover comprise, as additional component, at leastone heat stabilizer, an example being pentaerythritoltetrakis[3-(3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl)propionate],octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, or else4,4′-bis(1,1-dimethylbenzyl)diphenylamine.

The fillers are generally inorganic or mineral fillers and canadvantageously have reinforcing, extending, or else flame-retardanteffect. At least at their surfaces, they bear groups which can reactwith the alkoxy groups of the unsaturated organosilane/mixtures. Theresult of this can be that the silicon atom, with the functional groupbonded thereto, becomes chemically fixed on the surface. Particularexamples of groups of this type on the surface of the filler are hydroxygroups.

Preferred fillers are accordingly metal hydroxides having astoichiometric proportion of hydroxy groups or, in the variousdehydrated forms thereof, having a substoichiometric proportion ofhydroxy groups, extending as far as oxides having comparatively fewresidual hydroxy groups, where these are however detectable by DRIFT-IRspectroscopy.

Examples of suitable fillers are aluminum trihydroxide (ATH), aluminumoxide hydroxide (AlOOH.aq), magnesium dihydroxide (MDH), brucite,huntite, hydromagnesite, mica, and montmorillonite. Other fillers thatcan be used are calcium carbonate, talc, and also glass fibers. It isalso possible to use the materials known as “char formers”, examplesbeing ammonium polyphosphate, stannates, borates, talc, or materials ofthese types in combination with other fillers.

The composition may comprise, as further component e), a thermoplasticparent polymer, a silane-grafted parent polymer, a silane-copolymerizedparent polymer, and/or monomers and/or prepolymers of said parentpolymers, or else silane block coprepolymers or block coprepolymers,and/or a mixture of these. It is preferable that the thermoplasticparent polymer is a nonpolar polyolefin, an example being polyethyleneor polypropylene, or a polyvinyl chloride, or a silane-graftedpolyolefin and/or silane-copolymerized polyolefin, and/or a copolymer ofone or more olefins and of one or more comonomers which contain polargroups.

The thermoplastic parent polymer can also function to some extent orcompletely as carrier material, for example in a masterbatch,comprising, as carrier material, a thermoplastic parent polymer or apolymer and the silicon-containing precursor compound of an organic acidand an organofunctional silane compound or, in an alternative, athermoplastic parent polymer, or a polymer and an organofunctionalsilane compound, in particular of the formula III, and an organic acid.

Other examples of silane-copolymerized thermoplastic parent polymers areethylene-silane copolymers, for example ethylene-vinyltrimethoxysilanecopolymer, ethylene-vinyltriethoxysilane copolymer,ethylene-dimethoxyethoxysilane copolymer,ethylene-gamma-trimethoxysilane copolymer,ethylene-gamma-(meth)acryloxypropyltriethoxysilane copolymer,ethylene-gamma-acryloxypropyltriethoxysilane copolymer,ethylene-gamma-(meth)acryloxypropyltrimethoxysilane copolymer,ethylene-gamma-acryloxypropyltrimethoxysilane copolymer, and/orethylene-triacetoxysilane copolymer.

The nonpolar thermoplastic parent polymers used can comprisethermoplastics such as in particular an unmodified PE grade, an examplebeing LDPE, LLDPE, HDPE, or mPE. Parent polymers bearing polar groupsgive by way of example improved fire performance, i.e. lowerflammability and smoke density, and increase capability to acceptfiller. Examples of polar groups are hydroxy, nitrile, carbonyl,carboxy, acyl, acyloxy, and carboalkoxy groups, and amino groups, andalso halogen atoms, in particular chlorine atoms. Olefinic double bondsand carbon-carbon triple bonds are nonpolar. Suitable polymers are notonly polyvinyl chloride but also copolymers of one or more olefins andof one or more comonomers which contain polar groups, e.g. vinylacetate, vinyl propionate, (meth)acrylic acid, methyl(meth)acrylate,ethyl(meth)acrylate, butyl(meth)acrylate, or acrylonitrile. Examples ofthe amounts of the polar groups in the copolymers are from 0.1 to 50 mol%, preferably from 5 to 30 mol %, based on the polyolefin units.Particularly suitable parent polymers are ethylene-vinyl acetatecopolymers (EVA). By way of example, a suitable commercially availablecopolymer contains 19 mol % of vinyl acetate units and 81 mol % ofethylene units.

Particularly suitable parent polymers are polyethylene, polypropylene,and also corresponding silane-modified polymers. In particular,therefore, the use of inventive compositions or masterbatches (masterkitor polymer kit) can give silane-grafted, silane-copolymerized, and/orsilane-crosslinked PE, PP, polyolefin copolymer, EVA, EPDM, or EPM in anadvantageous manner. The silane-grafted polymers can be in a form filledwith fillers or in an unfilled form and, if appropriate, can bemoisture-crosslinked subsequently, after a shaping process. Acorresponding situation applies to the silane-copolymerized polymers ina form filled with fillers or in unfilled form, and these polymers can,if appropriate, be moisture-crosslinked subsequently, after a shapingprocess.

The composition of the invention is suitable as additive in a monosilprocess, in a sioplas process, and/or in a copolymerization process. Itis particularly appropriate that the silane hydrolysis catalyst and/orsilanol condensation catalyst does not become active until additionalmoisture is added. The final crosslinking of the unfilled or filledpolymer therefore generally takes place in a known manner in awaterbath, in a steam bath, or else via atmospheric moisture, at ambienttemperatures (the process known as “ambient curing”).

The form taken by the components of the composition, a particularexample being the silicon-containing precursor compound of an organicacid, is advantageously liquid and preferably waxy or solid, or bound ona carrier material, and/or the form taken by the organofunctional silanecompound can be liquid, highly viscous, waxy, or solid, or bound on acarrier material. In particular, the silicon-containing precursorcompound of an organic acid is in essence waxy or solid, i.e. is inessence in solid phase, which can have amorphous or crystalline regions.This measure can make it easy to store the precursor compound inanhydrous form, and to meter the precursor compound. Undesiredhydrolysis and/or condensation prior to use, in particular in a monosilprocess, sioplas process, or copolymerization process, can besuppressed.

In order to permit better regulation of metering capability and, ifappropriate, susceptibility to hydrolysis, the silicon-containingprecursor compound of an organic acid of the general formula I and/orII, the organofunctional silane compound and, if appropriate, thefree-radical generator can have been applied to a carrier material, forexample as described in EP 0 426 073.

To the extent that the silicon-containing precursor compound I and/or IIis itself solid, it can itself be used as carrier material, inparticular for an organofunctional silane, for example as a carriermaterial for a silane of the general formula III, for example ofvinyltriethoxysilane, vinyltrimethoxysilane,vinyltris(methoxyethoxy)silane (VTMOEO), vinyl (co)oligomers, or otherliquid silanes of the formula III.

Preferable suitable carrier material is a porous polymer selected frompolypropylene, polyolefins, ethylene copolymer using low-carbon alkenes,ethylene-vinyl acetate copolymer, high-density polyethylene, low-densitypolyethylene, or linear low-density polyethylene, where the porouspolymer can have a pore volume of from 30 to 90% and in particular canbe used in the form of granules or pellets.

As an alternative, the carrier material can also be a filler oradditional substance, in particular a nanoscale filler. Preferredcarrier materials, fillers, or additional substances are aluminumhydroxide, magnesium hydroxide, fumed silica, precipitated silica,wollastonite, calcined variants, chemically and/or physically modifiedmaterials, such as kaolin, modified kaolin, and in particular ground,exfoliating materials, such as phyllosilicates, preferably specifickaolins, a calcium silicate, a wax, such as a polyolefin wax based onLDPE (low-density polyethylene), or a carbon black.

The carrier material can encapsulate the silicon-containing precursorcompound and/or the silane compound of group a), and/or the free-radicalgenerator, or can retain these in physically or chemically bound form.It is advantageous here if the loaded or unloaded carrier material isswellable, in particular in a solvent. The amount of the silanecomponents of group a) is usually in the range from 0.01% by weight to99.9% by weight, preferably from 0.1% by weight to 70% by weight,preferably from 0.1% by weight to 50% by weight, with particularpreference from 0.1% by weight to 30% by weight, based on the totalweight of the composition comprising the carrier material, particularlypreferably in the form of masterbatch. The amount present of the carriermaterial is therefore generally from 99.99 to 0.01% by weight, based onthe total weight of the composition (giving 100% by weight).

In order to facilitate metering of the composition and protect it frompremature hydrolysis, it is particularly preferable that thesilicon-containing precursor compound of an organic acid, theorganofunctional silane compound, or a mixture of the two compounds isin a form that is waxy or solid or bound to a carrier material.

Individual preferred carrier materials that may be mentioned are: ATH(aluminum trihydroxide, Al(OH)₃), magnesium hydroxide (Mg(OH)₂), orfumed silica, which is produced on an industrial scale via continuoushydrolysis of silicon tetrachloride in a hydrogen/oxygen flame. Thisprocess vaporizes the silicon tetrachloride which then reactsspontaneously and quantitatively within the flame with the water derivedfrom the hydrogen/oxygen reaction. Fumed silica is an amorphous form ofsilicon dioxide and is a free-flowing, bluish powder. Particle size isusually in the region of a few nanometers, and specific surface area istherefore large, generally being from 50 to 600 m²/g. The process bywhich the vinylalkoxysilanes and/or the silicon-containing precursorcompound, or a mixture of these, becomes attached to the material hereis therefore in essence adsorption. Precipitated silicas are generallyproduced from sodium waterglass solutions, via neutralization withinorganic acids under controlled conditions. After isolation from theliquid phase, washing, and drying, the crude product is finely ground,e.g. in steam-jet mills. Again, precipitated silica is a substantiallyamorphous silicon dioxide, the specific surface area of which isgenerally from 50 to 150 m²/g. Unlike fumed silica, precipitated silicahas a certain porosity, for example about 10% by volume. The process bywhich the vinylalkoxysilanes and/or the silicon-containing precursorcompound, or a mixture of these, becomes attached to the material cantherefore be either adsorption on the surface or absorption within thepores. Calcium silicate is generally produced industrially by fusingquartz or kieselguhr with calcium carbonate or calcium oxide, or viaprecipitation of aqueous sodium metasilicate solutions withwater-soluble calcium compounds. The carefully dried product isgenerally porous and can absorb up to five times the amount by weight ofwater or oils.

Porous polyolefins, such as polyethylene (PE) or polypropylene (PP), andalso copolymers, such as ethylene copolymers with low-carbon alkenes,such as propene, butene, hexene, or octene, or ethylene-vinyl acetate(EVA) are produced via specific polymerization techniques andpolymerization processes. Particle sizes are generally from 3 to <1 mm,and porosity can be above 50% by volume, and the products can thereforeabsorb suitably large amounts of unsaturated organosilane/mixtures, forexample of the general formula III, and/or of the silicon-containingprecursor compound, or a mixture of these, without losing theirfree-flow properties.

Particularly suitable waxes are polyolefin waxes based on low-densitypolyethylene (LDPE), preferably branched, with long side chains. Themelting and freezing point is generally from 90 to 120° C. The waxesgenerally give good results in mixing with the unsaturatedorganosilanes, such as vinylalkoxysilane, and/or with thesilicon-containing precursor compound, or a mixture of these, in alow-viscosity melt. The solidified mixture is generally sufficientlyhard to be capable of granulation.

The various commercially available forms of carbon black are suitable byway of example for producing black cable sheathing.

The following methods inter alia are available for producing thecompositions (dry liquids) on carriers, examples being compositions madeof olefinic silane carboxylates, such as vinylsilane carboxylate ofmyristic acid or lauric acid, and carrier material, or else ofvinylsilane stearate and carrier material, or of a tetracarboxysilaneand vinylalkoxysilane with carrier material:

Among the best-known methods is spray drying. Alternative methods areexplained in more detail below: mineral carriers or porous polymers aregenerally preheated, e.g. to 60° C. in an oven, and charged to acylindrical container which has been flushed with, and filled with, drynitrogen. A vinylalkoxysilane and/or vinylcarboxysilane is generallythen added, and the container is placed in a roller apparatus whichrotates it for about 30 minutes. After this time, the carrier substanceand the liquid, high-viscosity or waxy alkoxysilane and/or carboxysilanehave usually formed flowable, dry-surface granules which areadvantageously stored under nitrogen in containers impermeable to light.As an alternative, the heated carrier substance can be charged to amixer flushed and filled with dry nitrogen, e.g. a plowshare mixer ofLODIGE type or a propeller mixer of HENSCHEL type. The mixer element canthen be operated and the olefinic alkoxysilane and/or carboxysilane, inparticular of the formula I, or a mixture of these, can be sprayed in byway of a nozzle once the maximum mixing rate has been reached. Whenaddition has been completed, homogenization generally continues for afurther approximately 30 minutes, and the product is then dischargedinto nitrogen-filled containers impermeable to light, for example bymeans of a pneumatic conveying system operated with dry nitrogen.

Polyethylene wax or any other wax in pelletized form with a meltingpoint of from 90 to 120° C. or above can be melted in portions in aheatable vessel with stirrer, reflux condenser, and liquid-additionapparatus, and maintained in the molten state. Dry nitrogen is suitablypassed through the apparatus during the entire production process. Byway of the liquid-addition apparatus it is possible by way of example toadd the liquid vinylcarboxysilane/mixtures progressively to the melt andmix these with the wax by vigorous stirring. The melt is then generallydischarged into molds to solidify, and the solidified product isgranulated. As an alternative, the melt can be allowed to drip onto acooled molding belt on which it solidifies in the form of user-friendlypastilles.

The invention also provides a masterkit, in particular comprising acomposition described above, where the masterkit comprises, as componentA

-   -   from 0.1 to 20% by weight, in particular from 0.1 to 10% by        weight, preferably from 0.1 to 5% by weight, particularly        preferably from 0.1 to 3% by weight, preferably from 0.5 to 5%        by weight, in component A, of at least one silicon-containing        precursor compound of an organic acid, in particular of the        general formula I and/or II as defined above, or at least one        organic acid, or one silicon-free precursor compound comprising        an organic acid, in particular as defined above, and a carrier        material making up 100% by weight of component A, or    -   in alternatives, also a stabilizer, an added substance, or a        mixture of these, making up 100% by weight of component A, and    -   if appropriate, as component B, from 60 to 99.9% by weight, in        component B, of an organofunctional silane compound of the        formula III, where the definitions of b, a, B, R⁴, and R⁵ are as        above, and also    -   if appropriate from 0.05 to 10% by weight of a free-radical        generator, and    -   if appropriate from 0.05 to 10% by weight of at least one        stabilizer, and/or    -   from 0.05 to 99.99% by weight of at least one carrier material,        stabilizer, added substance, or a mixture of these, where added        substances that can be used comprise fillers and additives or a        mixture of these, where the quantitative data give a total of        100% by weight in component B. Suitable added substances have        been described above.

Particular carrier materials that can be used are those mentioned above,examples being PE, PP, and also others mentioned above. Similarconsiderations apply to the free-radical generator and to thestabilizer. Components A and B are preferably present separately fromone another within the masterkit where the intention is to use them intwo steps of the process. In the case of simultaneous use, the twocomponents A and B can be present together in a physical mixture, forexample in the form of powder, granules, or pellets, or else can bepresent in a single formulation, for example in pellet form or tabletform. A masterbatch of the invention comprises a vinyltriethoxysilane,for example vinyltrimethoxysilane, a peroxide, and also a processingaid, and also a silicon-containing precursor compound of an organicacid, if appropriate with a carrier material.

One preferred masterkit comprises by way of example 2% by weight of anorganic acid, such as a fatty acid, in particular myristic acid, orlauric acid, on a polymeric carrier material, such as HDPE, where theamount of HDPE present is 98% by weight of the masterkit (component A),making up the balance of 100% by weight. Other masterkits comprise asorganic acid preferably behenic acid, L-leucine, capric acid, oleicacid, lauric acid, and/or myristic acid, if appropriate in a mixture ona carrier material, for example HDPE.

The component B present can preferably comprise an unsaturatedalkoxysilane, in particular of the formula III, or oligomeric siloxanesproduced therefrom, preferably vinyltrimethoxysilane orvinyltriethoxysilane, together with a free-radical generator and with astabilizer, if appropriate with further additives. Preferably on acarrier material, for example in the form of granules.

The invention also provides a process for producing compounded polymermaterials, examples being granules, finished products, and moldings, inparticular of unfilled or filled polymers, by

-   -   1) reacting a mixture made of thermoplastic parent polymer, in        particular with a component of group a) at least one        silicon-containing precursor compound of an organic acid and/or        one organofunctional silane compound and, if appropriate, in        particular with a component of group b) an organic acid, a        silicon-free precursor compound containing an organic acid, and        also a free-radical generator, in a compounding apparatus, in        particular in the presence of moisture, or    -   2) reacting a mixture made of thermoplastic parent polymer, in a        first step, with a) an organofunctional silane compound, and        also a free-radical generator, in particular for producing        silane-grafted polymer, and shaping the material, in a        subsequent, in particular immediately subsequent, step, with        addition of at least one silicon-containing precursor compound        of an organic acid, one organic acid, and/or one silicon-free        precursor compound containing an organic acid, and crosslinking        the material with exposure to moisture, or    -   3) reacting a mixture made of thermoplastic parent polymer, in a        first step, with a) at least one olefinic silicon-containing        precursor compound of an organic acid, in particular of the        general formulae I and/or II, where z=1, 2, or 3, and also with        a free-radical generator, and shaping the material, in a        subsequent step, with addition of at least one        silicon-containing precursor compound of an organic acid, one        silicon-free precursor compound containing an organic acid,        and/or one organic acid, and crosslinking the material with        exposure to moisture, or    -   4) reacting a mixture made of monomer and/or prepolymer of the        thermoplastic parent polymers with a) an organofunctional silane        compound, and also a free-radical generator, in particular for        producing silane-copolymerized parent polymer, and shaping the        material, in a subsequent, in particular immediately subsequent        or nearly subsequent, step, with addition of at least one        silicon-containing precursor compound of an organic acid, one        organic acid, and/or one silicon-free precursor compound        containing an organic acid, and then crosslinking the material        with exposure to moisture.

In an alternative process of the invention for producing compoundedpolymer materials, such as granules, finished products, moldings, and inparticular unfilled or filled polymers,

-   -   1) a mixture made of thermoplastic parent polymer is reacted        with component B of the masterkit and component A of the        masterkit described above in a compounding apparatus, and if        appropriate is shaped at a given juncture, and crosslinked by        moisture, or    -   2) a mixture made of thermoplastic parent polymer is reacted, in        a first step, with component B of the masterkit described above        and, in a subsequent step, is shaped, with addition of component        A of a masterkit described above, and is crosslinked with        exposure to moisture, or    -   3) a mixture made of monomer and/or prepolymer of the        thermoplastic parent polymers is reacted with component B of the        masterkit, as described in the introduction, and is shaped, in a        subsequent step, with addition of component A of the masterkit,        and is then crosslinked with exposure to moisture, and in        particular a thermoplastic parent polymer is mixed with        component B of the masterkit and reacted, and then granulated        and, if appropriate, drawn off or packed by way of example in        the form of PEg (PE granules) in an aluminum-coated sack. In a        subsequent step, component A is added to the granules (PEg), and        mixed, and if appropriate shaped, and during this process or        subsequently crosslinked in the presence of moisture; or    -   4) a mixture made of thermoplastic parent polymer is reacted        with the composition described above or with a masterkit        described above in a monosil process, in particular one of the        abovementioned preferred compositions, or    -   5) a mixture made of thermoplastic parent polymer is reacted        with the composition described above, or with a masterkit        described above, in a sioplas process, or    -   6) a mixture made of monomer and/or prepolymer of the        thermoplastic parent polymers is reacted with a composition        described above or with a masterkit described above, in a        copolymerization process.

The invention also provides the reaction of a polymer kit, in particularas claimed in claim 15, in a monosil process or sioplas process, or in acopolymerization process.

One embodiment of the invention uses the composition described above, inparticular as claimed in claims 1 to 8, and/or the masterkit, or thepolymer kit, in the production of silane-grafted, silane-copolymerized,and/or crosslinked, in particular siloxane-crosslinked, filled orunfilled polymers.

The invention also provides the use of the composition or of themasterkit, or of the polymer kit, in particular in a monosil, sioplas,or copolymerization process, for producing filled and/or unfilledcompounded polymer materials, which can take crosslinked oruncrosslinked form, and/or of crosslinked filled and/or unfilledpolymers based on thermoplastic parent polymers. For the purposes of theinvention, crosslinking in particular means the formation of anSi—O-substrate bond or Si—O-filler or Si—O-carrier material, or Si—O'Sibridging, i.e. the condensation of an Si—OH group with a condensableother group of a substrate.

Preference is given to the use for the production of silane-grafted,silane-copolymerized, and/or crosslinked, in particularsiloxane-crosslinked, filled or unfilled polymers. The abovementionedpolymers can also comprise block copolymers. It is preferable that thefillers are likewise crosslinked with the silicon-containing compounds,in particular by way of an Si—O-filler/carrier material bond. Particularfillers that can be used are the abovementioned fillers or carriermaterials. In some of the abovementioned processes, it is preferable touse the unsaturated fatty acids. There are therefore sometimes noconventional organic acids used, examples being acetic acid, formicacid, maleic acid, maleic anhydride, or stearic acid.

The process as claimed in claim 10 paragraph 1) is preferably conductedwith at least one monounsaturated alkoxysilane corresponding to theformula III or one silicon-containing precursor compound of an organicacid, in particular of the formulae I and/or III, or with a mixture ofthe abovementioned compounds.

Preferred silicon-containing precursor compounds of the general formulaeI and/or II are compounds where R¹ is a carbonyl-R³ group selected fromthe group of the natural saturated and unsaturated fatty acids, inparticular having hydrophobic hydrocarbon moieties having from 4 to 45carbon atoms, in particular having from 6 to 45 carbon atoms, inparticular having from 6 to 22 carbon atoms, preferably having from 8 to22 carbon atoms, particularly preferably having from 6 to 14 carbonatoms, with particular preference where R³ is from 11 to 13 carbonatoms, particularly preferably where z is 0 or 1. It can be preferableto use, in compositions, a monounsaturated alkoxysilane together with acompound of the formula I and/or II, where z is 0, 1, 2, or 3.

Preferred organic acids used for the thermoplastic parent polymers, orthe silane-grafted and/or silane-copolymerized parent polymers, but inparticular not for polyvinyl chlorides, are fatty acids selected fromthe group of the natural saturated and mono- or polyunsaturated fattyacids, in particular having hydrophobic hydrocarbon moieties having from4 to 45 carbon atoms, in particular having from 6 to 45 carbon atoms inR³, in particular having from 6 to 22 carbon atoms, preferably havingfrom 8 to 22 carbon atoms, particularly preferably having from 6 to 14carbon atoms,

with particular preference where R³ is from 11 to 13 carbon atoms,particularly preferably myristic acid and/or lauric acid. It can bepreferable, in particular in a single-step process, to use, either aloneor in compositions, a mono- or polyunsaturated alkoxysilane where a is0, with no other alkylsilane.

The moisture-crosslinked unfilled or filled compounded polymer materialsof the invention are generally produced via appropriate mixing of therespective starting-material components in the melt, as explained abovefor the processes, advantageously with exclusion of moisture. The usualheatable homogenization apparatuses are generally suitable for thispurpose, examples being kneaders or advantageously for continuousoperation Buss cokneaders or twin-screw extruders. As an alternative tothese, it is also possible to use a single-screw extruder. A possiblemethod here introduces the components continuously, in each caseindividually or in partial mixtures, in the prescribed quantitativeproportion, to the extruder, which has been heated to a temperatureabove the melting point of the thermoplastic parent polymer. It isadvantageous that the temperature rises in the direction toward the endof the screw, in order to establish a low viscosity and thus permitintensive mixing. In an advantageous method, the extrudates are stillliquid when they are introduced to an apparatus for the molding ofgranules or of moldings, such as pipes. The final crosslinking of theunfilled or filled polymer generally takes place in a known manner in awaterbath, in a steam bath, or else via atmospheric moisture at ambienttemperatures (the process known as “ambient curing”).

At least one stabilizer and/or at least one further added substance,corresponding to the statements above, can be added in the process ofthe invention, prior to and/or during the process, and/or during onestep of the process.

The invention also provides a polymer, for example a crosslinked filledor crosslinked unfilled polymer; a compounded polymer material, such asa compounded cable material, or a flame-retardant cable, for examplefilled with Mg(OH)₂ or Al(OH)₃, or with exfoliating materials, such asphyllosilicates; a filled plastic, an unfilled plastic and/or a moldingand/or article obtainable by the process of the invention, in particularas claimed in any of claims 10 to 12. Appropriate moldings and/or itemsare cables, pipes, such as drinking-water lines, or products which canbe used in the food-and-drinks sector or in the sector of hygieneproducts, or in the sector of medical technology, for example as medicalinstrument or part of a medical instrument, Braunüle, trocar, stent,clot retriever, vascular prosthesis, or component of a catheter, tomention just a few possibilities.

The invention further provides a polymer kit comprising the compositiondescribed above, in particular the components of group a), b), c),and/or d), and also, in particular separately from these, in the form offurther component, component e) a thermoplastic parent polymer, anexample being a silane-grafted parent polymer or silane-copolymerizedparent polymer, or a monomer or prepolymer of the parent polymer, and/ora mixture of these. Components of group a), b), c), and/or d) canrespectively be separated or, supported on a carrier in the polymer kit,can take the form of a mixture on fillers or on mineral carriermaterials, for example on the abovementioned carrier materials, or elseon carbon, an example being activated charcoal or carbon black.

An alternative polymer kit comprises the masterkit described above andalso, as further component, a thermoplastic parent polymer, an examplebeing a silane-grafted parent polymer or silane-copolymerized parentpolymer, or a monomer or prepolymer of the parent polymer, and/or amixture of these.

An example of a polymer kit is: 63.5% by weight of HDPE, 1.5% by weightof myristic acid, 5% by weight of Irganox 1010 (methyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate), and 30% by weight ofPrintex alpha pigment.

In the case of single-stage processes, for example in the case of themonosil process, the polymer and the composition that initiatescrosslinking, the masterkit, or, in an alternative, the polymer kitonly, are charged to the extruder, and the resultant melt is processedin one step to give the final product. The inventive composition used isappropriately a composition which comprises an organofunctional silanecompound, in particular of the formula III, and which comprises afree-radical generator, and which also comprises a silicon-containingprecursor compound of an organic acid or comprises an organic acid, andalso, if appropriate, comprises a stabilizer.

For the production of filled plastics, the inorganic filler is mostlyintroduced directly to the compounding assembly and processed with thepolymer to give the final product. The filler can also optionally beintroduced at a later juncture into the assembly, for example in thecase of a twin-screw extruder or cokneader. The graft polymer producedusing the inventive composition or the inventive masterkit can givemarkedly better compatibility of nonpolar polymer and polar filler, forexample aluminum hydroxide or magnesium hydroxide.

It is also possible to produce a graft polymer, in particular sioplasmaterial, separately and, if appropriate, to granulate and package thematerial, in particular with protection from moisture, and to store thesame and then to supply the same as feedstock to a processor, forexample a cable producer or pipe producer, who in turn incorporatesfillers to produce final filled plastics products.

The following examples provide further illustration of the inventivecompositions, the masterkit, the polymer kit, and the inventiveprocesses, but the invention is not restricted to these examples.

A) Production of alkyl- or alkenyltricarboxysilane, ortetracarboxysilane GENERAL EXAMPLES

-   -   a) For the production of alkenyltricarboxysilane, 1 mol of an        alkenyltrichlorosilane, or in general terms an        alkenyltrihalosilane, is reacted directly with 3 mol, or with an        excess, of the organic monocarboxylic acid, or reacted in an        inert solvent, in particular at elevated temperature.    -   b) For the production of an alkyltricarboxysilane, 1 mol of an        alkyltrichlorosilane is correspondingly reacted directly with 3        mol, or with an excess, of an organic monocarboxylic acid, or is        reacted in an inert solvent. It is preferable that the reaction        takes place at elevated temperature, for example at up to the        boiling point of the solvent, or at around the melting point of        the organic fatty acid or of the organic acid.    -   c) For the production of tetracarboxysilanes, 1 mol of        tetrahalosilane, in particular tetrachlorosilane or        tetrabromosilane, is reacted with 4 mol, or with an excess, of        at least one monocarboxylic acid, for example one fatty acid or        fatty acid mixture. The reaction can take place directly via        melting or in an inert solvent, preferably at elevated        temperature.

Example 1 Production of vinyltristearylsilane

Reaction of 1 mol of vinyltrichlorosilane with 3 mol of stearic acid intoluene as solvent: 50 g of stearic acid (50.1 g) were used as initialcharge with 150.0 g of toluene in a flask. The solid dissolves aftergentle heating. Cooling gives a cloudy, highly viscous mass, which whenreheated again forms a clear liquid. The oil bath was set to 95° C. atthe start of the experiment, and about 20 minutes of mixing time gave aclear liquid. 9.01 g of vinyltrichlorosilane were then rapidly addeddropwise with a pipette. After about 10 min the mixture was a clearliquid, and the oil temperature was adjusted to 150° C. After about afurther 3 h after the start of the experiment, the mixture was cooledunder inert gas. It was worked up by distillative removal of thetoluene. This gave a white solid which when melted had an oily andyellowish appearance. For further purification, the solid can besubjected to further rotary evaporator treatment, for example for aprolonged period (3-5 h) at an oil bath temperature of about 90° C. andat a vacuum<1 mbar. The solid was characterized as vinyltrichlorosilaneby way of NMR (¹H, ¹³C, ²⁹Si).

Example 2 Production of vinyltridecanoic acid

Reaction of 1 mol of vinyltrichlorosilane with 3 mol of capric acid intoluene as solvent: 60.0 g of capric acid (decanoic acid) were used asinitial charge with 143.6 g of toluene in a flask. The oil bath was setto 80° C. at the start of the experiment, and the vinyltrichlorosilanewas slowly added dropwise (about 0.5 h for 19.1 g) while the temperatureof the mixture was about 55° C. After about 45 min, the temperature ofthe oil was increased to 150° C. After a reaction time of about afurther 2 h, the oil bath was switched off, but the stirring, thewater-cooling, and the nitrogen blanketing were continued until coolingwas complete. The clear liquid was transferred to a single-necked flask,and the toluene was drawn off in a rotary evaporator. The oil bathtemperature was set to about 80° C. The vacuum was adjusted stepwise to<1 mbar. The product was a clear liquid. The liquid was characterized asvinyltricaprylsilane by way of NMR (1H, ¹³C, ²⁹Si).

Example 3 Production of hexadecyltricaprylsilane

Reaction of 1 mol of Dynasylan® 9016 (hexadecyltrichlorosilane) with 3mol of capric acid in toluene as solvent: 73.1 g of capric acid(decanoic acid) were used as initial charge with 156.2 g of toluene in aflask. The oil bath was set to 95° C. at the start of the experiment,and 50.8 g of Dynasylan® 9016 were added dropwise over a period of about25 minutes. After about min, the temperature of the oil was increased to150° C. The experiment was terminated after reflux for about 1.5 h. Thetoluene was drawn off from the clear liquid in a rotary evaporator. Theoil bath temperature was set to about 80° C. The vacuum was adjustedstepwise to <1 mbar. The product was a yellow oily liquid with aslightly pungent odor. The liquid was characterized in essence ashexadecyltricaprylsilane by way of NMR (¹H, ¹³C, ²⁹Si).

Example 4 Production of vinyltripalmitylsilane

Reaction of 1 mol of vinyltrichlorosilane with 3 mol of palmitic acid intoluene as solvent: 102.5 g of palmitic acid were used as initial chargewith 157.0 g of toluene in a flask. The oil bath was set to 92° C. atthe start of the experiment, and the 22.0 g of vinyltrichlorosilane wereslowly added dropwise over a period of about 15 minutes. After about 70min, the temperature of the oil was increased to 150° C. The mixture washeated at reflux for about 4 h, and then the toluene was removed bydistillation. The oil bath temperature was adjusted to about 80° C., andthe vacuum was adjusted stepwise to 2 mbar. Cooling of the product gavea white, remeltable solid. The solid was characterized asvinyltripalmitylsilane by way of NMR (¹H, ¹³C, ²⁹Si).

Example 5 Production of chloropropyltripalmitylsilane

Reaction of 1 mol of CPTCS (chloropropyltrichlorosilane) with 3 mol ofpalmitic acid in toluene as solvent: 40.01 g of palmitic acid were usedas initial charge in a three-necked flask, and the oil bath was heated.Once all of the palmitic acid had dissolved, 11.03 g of the CPTCS(99.89% purity (GC/TCD)) were added dropwise within a period of about 10min. The temperature was finally increased to 130° C. After about 3.5 hno further gas activity was observed in an attached gas-washer bottle,and the synthesis was terminated. The toluene was removed in a rotaryevaporator. At a subsequent juncture, the solid was remelted and stirredat an oil bath temperature of about 90° C. under a vacuum of <1 mbar.After about 4.5 h, no further gas bubbles were observed. The solid wascharacterized as chloropropyltripalmitylsilane by way of NMR (¹H, ¹³C,²⁹Si).

Example 6 Production of propyltrimyristylsilane

Reaction of 1 mol of PTCS (propyltrichlorosilane, 98.8% purity) with 3mol of myristic acid in toluene as solvent. The reaction was analogousto that in the above examples. The reaction product was characterized aspropyltrimyristylsilane.

Example 7 Production of vinyltrimyristylsilane

Reaction of Dynasylan® VTC with myristic acid: 40.5 g of myristic acidand 130 g of toluene are used as initial charge in the reaction flask,and mixed and heated to about 60° C. 9.5 g of Dynasylan® VTC are addeddropwise within a period of 15 min by means of a dropping funnel. Thetemperature in the flask increases by about 10° C. during addition.After addition, stirring is continued for 15 minutes, and then thetemperature of the oil bath is increased to 150° C. During the continuedstirring, gas evolution (HCL gas) can be observed. Stirring wascontinued until no further gas evolution was observed (gas dischargevalve), and stirring was continued for 3 h. After cooling of themixture, unreacted Dynasylan® VTC and toluene were removed bydistillation at about 80° C. at reduced pressure (0.5 mbar). The productremaining in the reaction flask is stored overnight in the flask with N₂blanketing and then discharged without further work-up. The productsubsequently solidifies. About 44.27 g of crude product were obtained.

Example 8 Production of propyltrimyristylsilane

Reaction of Dynasylan® PTCS with myristic acid: 40.5 g of myristic acidand 150 g of toluene are used as initial charge in the reaction flask,and mixed and heated to about 60° C. Dynasylan® PTCS is added dropwisewithin a period of 15 minutes by means of a dropping funnel. Thetemperature in the flask increases by about 10° C. during addition.After addition the temperature of the oil bath is increased to 150° C.and stirring is continued for 3 h. During the continued stirring, gasevolution, HCL gas, can be observed. Stirring was continued until nofurther gas evolution was observed at the gas discharge valve. Aftercooling of the mixture, unreacted Dynasylan® PTCS and toluene wereremoved by distillation at about 80° C. at reduced pressure (0.5 mbar).The product was stored under inert gas and solidified. About 44.0 g ofcrude product were obtained.

B) Crosslinking Examples

Dynasylan® SILFIN 24 (vinyltrimethoxy (VTMO), peroxide, and processingaid)

Example 9

Grafting of Dynasylan® SILFIN 24 HDPE with Masterbatch

Grafting of 95% by weight of Dynasylan® SILFIN 24 HDPE with 5% by weightof masterbatch, and crosslinking at 80° C. in a waterbath. Themasterbatch comprised 2% by weight of catalyst.

TABLE 1 Overview of starting materials and gel contents Gel [%] Gel [%]Gel [%] 4 h at 80° C. 22 h at 80° C. Catalyst 0 h Waterbath WaterbathBehenic acid 17 36 53 Tryptophan 9 18 34 L-phenylalanine 16 26 39L-leucine 1 30 46 Blind value 13 16 34 Caprylic acid 25 37 49 Oleic acid22 42 52 Capric acid 23 36 44 Stearic acid 24 44 56 Palmitic acid 25 3953 Myristic acid 23 37 49 Lauric acid 31 37 48

All of the fatty acids and amino acids tested accelerate a crosslinkingreaction within the silane-modified polymer.

Example 10

Grafting of Dynasylan® SILFIN 24 HDPE with Masterbatch

As Example 9, only with 0.2% by weight catalyst content within themasterbatch.

TABLE 2 Overview of starting materials and gel contents Gel [%] Gel [%]Gel [%] 4 h at 80° C. 22 h at 80° C. Catalyst 0 h Waterbath WaterbathBlind value 1.00 11 25.37 Stearic acid 34 54.08 62.35 Palmitic acid 2948.60 62.43

Example 11

Grafting of Dynasilan® SILFIN 24 HDPE with Masterbatch

As Example 9, only with 0.5% by weight catalyst content within themasterbatch.

TABLE 3 Overview of starting materials and gel contents Gel [%] Gel [%]Gel [%] 4 h at 80° C. 22 h at 80° C. Catalyst 0 h Waterbath WaterbathBlind value 1 11 25 Capric acid 39 60 60 Caprylic acid 39 60 61 Myristicacid 38 59 64 Behenic acid 37 58 64 Stearic acid 37 61 66 Oleic acid 4962 65 Palmitic acid 48 63 66 Tegokat 216 67 70 69 (DOTL)

Example 12

Grafting of Dynasylan® SILFIN 24 HDPE with Masterbatch

As Example 9, only with 1.0% by weight catalyst content within themasterbatch.

TABLE 4 Overview of starting materials and gel contents Gel [%] Gel [%]Gel [%] 4 h at 80° C. 22 h at 80° C. Catalyst 0 h Waterbath WaterbathBlind value 12.51 16.43 33.60 Behenic acid 16.64 35.71 52.97 Stearicacid 24.17 43.86 55.72 Oleic acid 22.38 41.78 52.37 Palmitic acid 24.7838.82 53.19 Myristic acid 23.08 37.40 48.97 Capric acid 22.91 35.7944.18 Tegokat 216 44.12 61.37 65.79 (DOTL) Caprylic acid 24.87 37.4049.26

Example 13

Grafting of Dynasylan® SILFIN 24 HPDE with Masterbatch

Silane-grafted HDPE is reacted with various amounts of added myristicacid.

TABLE 5 Overview of starting materials and gel contents, 1.2 phr ofDynasylan ® SILFIN 24 Gel [%] Gel [%] Gel [%] 4 h at 80° C. 22 h at 80°C. Catalyst 0 h Waterbath Waterbath Blind value 0 0 26 0.2% by weight 2960 70 of myristic acid 0.075% by weight 40 70 73 of DOTL 0.5% by weight33 68 75 of myristic acid 1.0% by weight 47 72 76 of myristic acid

Example 14

Grafting of Dynasylan® SILFIN 24 HPDE with Masterbatch

Silane-grafted HDPE is reacted with various amounts of added myristicacid.

TABLE 6 Overview of starting materials and gel contents, 1.4 phr ofDynasylan ® SILFIN 24 Gel [%] Gel [%] Gel [%] 4 h at 80° C. 22 h at 80°C. Catalyst 0 h Waterbath Waterbath Blind value −0.37 0.73 29.72 0.2% byweight 21.46 58.79 70.39 of myristic acid 0.075% by weight 38.97 70.9775.19 of DOTL 0.5% by weight 21.46 58.79 70.39 of myristic acid 1.0% byweight 37.69 70.16 76.02 of myristic acid

Example 15

Grafting of Dynasylan® SILFIN 24 HDPE with Masterbatch

Silane-grafted HDPE is reacted with various amounts of added myristicacid.

TABLE 7 Overview of starting materials and gel contents, 1.6 phr ofDynasylan ® SILFIN 24 Gel [%] Gel [%] Gel [%] 4 h at 80° C. 22 h at 80°C. Catalyst 0 h Waterbath Waterbath Blind value 0 2 35 0.2% by weight 2765 73 of myristic acid 0.075% by weight 44 73 78 of DOTL 0.5% by weight36 71 76 of myristic acid 1.0% by weight 56 77 78 of myristic acid

The above experiments provide evidence that myristic acid achieves gelcontents comparable to those achieved with DOTL. When myristic acid isused, the amount of exudation observed on the crosslinked products iszero to small, even at high concentrations.

The following catalyst was used for the above Examples to 15: 0.2, 0.5,and 1.0% by weight of catalyst content (myristic acid) and 0.075% byweight of DOTL (standard masterbatch), compared with a blind value.Grafted HDPE was produced here with 1.2; 1.4, and 1.6 phr of Dynasylan®SILFIN 24. In each case, the silane-grafted PE was mixed with 5% byweight of the catalyst masterbatch, and processed in the kneader. AHAAKE laboratory kneader was used for processing, and plaques were thencompression-molded at 200° C. and crosslinked at 80° C. in thewaterbath.

Processing Parameters:

Kneader, feed hopper, belt mold, belt take-off; filled feed zone,

Rotation rate: 30 rpm,

temperature profile: 140° C./3 min; 2 min at 210° C.; 210° C./5 min

Crosslinking time: 0 h, 4 h and 22 h

Example 16

Step A—Grafting of MG9641S HDPE from Borealis with Dynasylan® SILFIN 24Mixtures

The grafting took place in a (ZE 25) twin-screw extruder from Berstorff.The experiments produced strands. The crosslinking agent preparation wasin each case applied for 1 h to the PE in a mixing drum, after predryingat 70° C. for about 1 h. The grafted strands were granulated afterextrusion. The granules were packaged directly after the granulationprocess in bags coated with an aluminum layer and these were closed bywelding. Prior to the welding process, the granules were blanketed withnitrogen.

Processing parameters for the grafting reaction in the ZE 25

Temperature profile: −/150/160/200/200/210/210/210° C.

Rotation rate: about 100 rpm, addition: 1.5 phr of Dynasylan® SILFIN 24

Step B—Processing for the Crosslinking Study

The silane-grafted polyethylene was kneaded in a laboratory kneader(Thermo HAAKE, 70 cm³) with the respective catalyst (temperatureprofile: 140° C./3 min; 2 min up to 210° C.; 210° C./5 min, kneaderrotation rate: 30 rpm). The mixture was then pressed at 200° C. to givesheets. Crosslinking took place in a waterbath at 80° C. (4 h). The gelcontents of the crosslinked sheets were determined (8 h, p-xylene,Soxhlet extraction).

1) Screening with Various Fatty Acids as Catalyst at 0.5% by WeightConcentration in Comparison with Tin Catalyst

TABLE 8 Gel contents for the study with various fatty acids as catalystin comparison with tin catalyst Gel [%], 4 h at 80° C. CatalystWaterbath Comments No catalyst 11 Caprylic acid 60 strong, pungent odorMyristic acid 59 Stearic acid 61 waxy exudation on surface of specimenPalmitic acid 63 waxy exudation on surface of specimen Dioctyltin 70dilaurate

2) Screening with Fatty Acids, Precursor Compounds of the Fatty Acids,and Amino Acids

In each case 95% by weight of silane-grafted PE with 5% by weight ofcatalyst masterbatch, where the catalyst masterbatch comprised 98% byweight of HDPE and 2% by weight of catalyst (organic acid). The resultscan be found in table 9.

TABLE 1 Gel contents for the study with various catalysts Gel [%] 22 hat 80° C. Catalyst Waterbath Catalyst type No catalyst 34 — Magnesiumstearate 37 Organic-acid- containing, silicon-free precursor compound ofthe fatty acid L-leucine 46 Amino acid Hexadecyltripalmitic 49Silicon-containing acid silane precursor compound of a fatty acidBehenic acid 53 Fatty acid Tegokat 216 (DOTL) 66 Tin catalyst

Example 17

a) Grafting of MG9641S HDPE from Borealis with Dynasylan® SILFIN 24

The grafting took place in a ZE 25 extruder from Berstorff. Thecrosslinking agent preparation was in each case applied for 1 h to thePE in a mixing drum, after predrying at 70° C. for about 1 h. Thegrafted strands were granulated after extrusion. The granules werepackaged directly after the granulation process inpolyethylene-aluminum-polyethylene packaging and these were closed bywelding. Prior to the welding process, the granules were blanketed withnitrogen.

Processing Parameters for the Grafting Reaction in the ZE 25

Temperature profile: −/150/160/200/200/210/210/210° C.

Rotation rate: about 100 rpm,

Addition: 1.5 phr of Dynasylan® SILFIN 24 (CS/V039/08)

b) Kneading Processes

For the production of the masterbatch, 49.0 g of PE were kneaded in aHAAKE laboratory kneader with 1.0 g of catalyst, organic acid, orsilicon-containing precursor compound.

Processing Parameters:

Kneader, feed hopper, tape die, tape take-off; filled feed zone,

Rotation rate: 30 rpm,

Temperature profile: 200° C./5 min

c) Production of Mixture Made of 95% By Weight of Silfin 24 HDPE with 5%By Weight of Masterbatch

A mixture made of 95% by weight of Silfin 24 HDPE with 5% by weight ofthe masterbatch comprising the catalyst is produced. Processing tookplace in a HAAKE laboratory kneader. A mixture made of 95% by weight ofSilfin 24 HDPE mixture with 5% by weight of masterbatch is kneaded, thenpressed at 200° C. to give sheets, and finally crosslinked in awaterbath at 80° C.

Processing Parameters:

Kneader, feed hopper, tape die, tape take-off; filled feed zone,

Rotation rate: 30 rpm,

Temperature profile: 140° C./3 min; 2 min up to 210° C.; 210° C./5 min

Crosslinking time: 0 h, 4 h, and 22 h

Example 18

Crosslinking of Silane-Grafted HDPE

Polyethylene was modified chemically (grafted, rotation rate: 30 rpm,temperature profile: 3 min at 140° C., 2 min from 140° C. to 200° C., 10min 200° C.) with various vinylsilanes with addition of peroxide in aHAAKE data-gathering kneader. Once the graft reaction had beenconcluded, aluminum trihydroxide (ATH) was added to the kneader as waterdonor. The presence of postcrosslinking detectable by way of a markedincrease in torque was checked. The following mixtures were used:

TABLE 10 Experimental mixtures Dynasylan ® VinyltripalmiticVinyltricapric VTMO acid silane acid silane BCUP (tert-butyl  ~0.1 g~0.14 g ~0.1 cumyl peroxide) Silane-containing ~0.55 g  ~1.1 g ~1.3compound HDPE 50 g ATH  2 g

Both experiments using vinyltricarboxysilanes revealed a marked increasein torque after addition of the ATH. The increase was considerably moremarked than with vinyltrimethoxysilane. The conclusion from this is thatthe extent of crosslinking reaction is greater.

Example 19

Crosslinking of HDPE—Comparison of Vinyltripalmitic acid silane withDynasylan® SILFIN 06

For this study, the individual crosslinking preparations were admixedwith the HDPE power and processed in the kneader (rotation rate: 35 rpm,temperature profile: 2 min at 150° C., in 3 min from 150 to 210° C., 5min at 210° C.). Table 11 lists the formulations:

TABLE 11 Formulation Vinyltripalmitic acid silane DCUP (dicumylperoxide) 0.025 g Silane-containing compound 1.5 g HDPE 50 g

The kneaded specimen was pressed to give a sheet and then crosslinked at80° C. in the waterbath. The gel content of the crosslinked specimenswas measured after various storage times.

TABLE 12 Gel contents of crosslinked specimens Crosslinking time Gelcontent for Waterbath, 80° C. vinyltripalmitic acid silane [%] 0.5 h 321 h 32 2 h 31 4 h 33 24 h 31

Example 20

Masterkit (Masterbatch)

The carboxysilanes produced were used as catalysts in the sioplasprocess. For this, 95% by weight of a polyethylene grafted withDynasylan® SILFIN 24 were kneaded with 5% by weight of the catalystconcentrate (catMB) of the invention. First, a masterbatch was producedwith 1 g of the respective catalyst and 49 g of HDPE in the kneader(temperature profile: 5 min at 200° C.). 2.5 g of this were then kneadedtogether with 47.5 g of the extruded Dynasylan® SILFIN 24 HDPE(temperature profile: 3 min at 140° C., from 140° C. to 210° C. in 2min, 5 min at 210° C.), and then pressed at 200° C. to give sheets, andfinally crosslinked at 80° C. in the waterbath. The catMB includedrespectively 2% by weight of the respective catalyst, in particular ofthe vinyltricarboxysilanes or fatty acids. The results were comparedwith a mixture without catalyst. The sheets were crosslinked at 80° C.in the waterbath. Table 13 shows the results of this crosslinking study.

TABLE 13 Overview of catalyst study in the sioplas process Catalyst/ Gelcontent [%] Gel content [%] experiment Gel content [%] 4 h at 80° C. 22h at 80° C. number Uncrosslinked Waterbath Waterbath Blind value - 13 1634 no cat. Vinyltri- 17 33 46 palmitic acid silane Hexadecyltri- 18 4049 palmitic acid silane Vinyltricapric 23 36 46 acid silaneHexadecyltri- 23 39 45 capric acid silane Capric acid 23 36 44 Palmiticacid 25 39 53

1. A composition, comprising: a) at least one silicon-comprisingprecursor compound of an organic acid, and/or one organofunctionalsilane compound; and, optionally, b) one organic acid, and/or onesilicon-free precursor compound comprising an organic acid.
 2. Thecomposition of claim 1, wherein in a), i) the at least onesilicon-comprising precursor compound of an organic acid corresponds toformula I and/or II(A)_(z)SiR² _(x)(OR¹)_(4-z-x)   (I)(R¹O)_(3-y-u)(R²)_(u)(A)_(y)Si-A-Si(A)_(y)(R²)_(u)(OR¹)_(3-y-u)   (II),wherein mutually independently, z is 0, 1, 2, or 3, x is 0, 1, 2, or 3,y is 0, 1, 2, or 3, and u is 0, 1, 2, or 3, with the proviso that informula L z+x is smaller than or equal to (≦)3, and, in formula II, y+uis independently smaller than or equal to (≦)2, A is mutuallyindependently in formula I and/or II a monovalent olefin group, and A inthe form of a divalent moiety in formula II is a divalent olefin group,R¹ is, mutually independently, a carbonyl-R³ group, where R³ correspondsto a hydrocarbon moiety, having from 1 to 45 carbon atoms, and R²corresponds, mutually independently, to a hydrocarbon group, and/or ii)the organofunctional silane compound corresponds to an unsaturatedalkoxysilane of formula III(B)_(b)SiR⁴ _(a)(OR⁵)_(3-b-a)   (III), wherein mutually independently, bis 0, 1, 2, or 3, and a is 0, 1, 2, or 3, with the proviso that informula III, b+a is smaller than or equal to 3, B, mutuallyindependently, is a monovalent (R⁷)₂C═C(R⁷)-E_(q)- group in formula III,in which R⁷ are identical or different, and R⁷ is a hydrogen atom or amethyl group or a phenyl group, E is —CH₂—, —(CH₂)₂—, —(CH₂)₃—,—O(O)C(CH₂)₃—, or —C(O)O—(CH₂)₃—, q is 0 or 1, or isoprenyl, hexenyl,cyclohexenyl, terpenyl, squalanyl, squalenyl, polyterpenyl,betulaprenoxy, cis/trans-polyisoprenyl, or anR⁶-D_(p)-[C(R⁶)═C(R⁶)—C(R⁶)═C(R⁶)]_(t)-D_(p)- group, in which R⁶ areidentical or different, and R⁶ is a hydrogen atom or an alkyl grouphaving from 1 to 3 carbon atoms, or an aryl group, or an aralkyl group,groups D are identical or different, and D is —CH₂—, —(CH₂)₂—, —(CH₂)₃—,—O(O)C(CH₂)₃—, or —C(O)O—(CH₂)₃—, p is 0 or 1, and t is 1 or 2, R⁵ is,mutually independently, methyl, ethyl, n-propyl, or isopropyl, R⁴ is,mutually independently, a substituted or unsubstituted hydrocarbongroup.
 3. The composition of claim 1, wherein b) is present and, in b),the at least one organic acid is present and comprises at least oneselected from the group consisting of iii.a) a saturated fatty acid, andunsaturated fatty acid, a natural amino acid, a synthetic amino acid,iii.b) an acid-comprising silicon-free precursor compound, an anhydride,and an ester.
 4. The composition of claim 1, further comprising c), atleast one free-radical generator.
 5. The composition of claim 4, whereinthe at least one free-radical generator is selected from the groupconsisting of an organic peroxide and an organic perester.
 6. Thecomposition of claim 1, further comprising d), at least one selectedfrom the group consisting of a stabilizer and a further added substance.7. The composition of claim 1, further comprising e), a thermoplasticparent polymer, a silane-grafted parent polymer, or asilane-copolymerized parent polymer, and/or a monomer and/or prepolymerof said parent polymers, and/or a mixture of these.
 8. The compositionof claim 1, wherein the silicon-comprising precursor compound of anorganic acid is present and is in a form that is liquid, waxy, solid, orbound on a carrier material, and/or the organofunctional silane compoundis present and is in a form that is liquid, highly viscous, waxy, solid,or bound on a carrier material.
 9. A masterkit, comprising thecomposition of claim 1, comprising: as component A, 0.1 to 10% byweight, in component A, of the at least one silicon-comprising precursorcompound of an organic acid, or the at least one organic acid, or theone silicon-free precursor compound comprising an organic acid, ispresent, and, making up 100% by weight of component A, one carriermaterial, one stabilizer, one added substance, or a mixture of these,and optionally, as component B, from 60 to 99.9% by weight, in componentB, of the organofunctional silane compound of the formula III(B)_(b)SiR⁴ _(a)(OR⁵)_(3-b-a)   (III), wherein mutually independently, bis 0, 1, 2, or 3, and a is 0, 1, 2, or 3, with the proviso that, informula III, b+a is smaller than or equal to (≦)3, B, mutuallyindependently, is a monovalent (R⁷)₂C═C(R⁷)-E_(q)- group in formula III,in which R⁷ are identical or different, and R⁷ is a hydrogen atom or amethyl group or a phenyl group, E is —CH₂—, —(CH₂)₂—, —(CH₂)₂—,—O(O)C(CH)₃—, or —C(O)O—(CH₂)₂—, q is 0 or 1, or isoprenyl, hexenyl,cyclohexenyl, terpenyl, squalanyl, squalenyl, polyterpenyl,betulaprenoxy, cis/trans-polyisoprenyl, or anR⁶-D_(p)-[C(R⁶)═C(R⁶)—C(R⁶)═C(R⁶)]_(t)-D_(p)- group, in which R⁶ areidentical or different, and R⁶ is a hydrogen atom or an alkyl grouphaving from 1 to 3 carbon atoms, or an aryl group, or an aralkyl group,groups D are identical or different, and D is —CH₂—, —(CH₂)₂—, —(CH₂)₃—,—O(O)C(CH₂)₃—, or —C(O)O—(CH₂)₃—, p is 0 or 1, and t is 1 or 2, R⁵ is,mutually independently, methyl, ethyl, n-propyl, or isopropyl, R⁴ is,mutually independently, a substituted or unsubstituted hydrocarbongroup, and optionally, from 0.05 to 10% by weight of a free-radicalgenerator and, optionally, from 0.05 to 10% by weight of at least onestabilizer, and/or from 0.05 to 99.99% by weight of at least one carriermaterial, stabilizer, added substance, or a mixture of these, summing toa total of 100% by weight in component B.
 10. A process for producing acompounded polymer material, the process comprising: 1) reacting amixture comprising at least one thermoplastic parent polymer with a) atleast one silicon-comprising precursor compound of an organic acidand/or one organofunctional silane compound and, optionally, b) anorganic acid, a silicon-free precursor compound comprising an organicacid, and a free-radical generator, in a compounding apparatus, or 2)reacting the mixture, first, with a) the organofunctional silanecompound, and the free-radical generator, to give a material, andshaping the material subsequently, with addition of the at least onesilicon-comprising precursor compound of an organic acid, the onesilicon-free precursor compound comprising an organic acid, and/or theone organic acid, to give a second material, and crosslinking the secondmaterial by exposure to moisture, or 3) reacting the mixture first witha) at least one olefinic silicon-comprising precursor compound of anorganic acid, and the free-radical generator, to give a material andshaping the material in a subsequent step, with addition of the at leastone silicon-comprising precursor of an organic acid, the onesilicon-free precursor compound comprising an organic acid, and/or theone organic acid, to give a second material, and crosslinking the secondmaterial by exposure to moisture, or 4) reacting a different mixturecomprising at least one monomer and/or prepolymer of the at least onethermoplastic parent polymer with a) the organofunctional silanecompound, and the free-radical generator, to give a material, andshaping the material, subsequently, with addition of the at least onesilicon-comprising precursor compound of an organic acid, the oneorganic acid, and/or the one silicon-free precursor compound comprisingan organic acid, to give a second material, and then crosslinking thesecond material with exposure to moisture.
 11. A process for producing acompounded polymer material, the process comprising 1) reacting amixture comprising at least one thermoplastic parent polymer withcomponent B of the masterkit and component A of the masterkit of claim9, in a compounding apparatus, or 2) reacting the mixture firstcomponent B of the masterkit of claim 9, to give a material, and shapingthe material subsequently, with addition of component A of the masterkitof claim 9, and crosslinking the second material by exposure tomoisture, or 3) reacting a different mixture comprising at least onemonomer and/or prepolymer of the at least one thermoplastic parentpolymer with component B of the masterkit of claim 9, to give amaterial, and shaping the material subsequently, with addition ofcomponent A of the masterkit of claim 9, to give a second material, andthen crosslinking the second material by exposure to moisture, or 4)reacting the mixture with a composition comprising: a) at least onesilicon-comprising precursor compound of an organic acid, and/or oneorganofunctional silane compound; and, optionally, b) one organic acid,and/or one silicon-free precursor compound comprising an organic acid,or the masterkit of claim 9, in a monosil process, or 5) reacting themixture with a composition comprising: a) at least onesilicon-comprising precursor compound of an organic acid, and/or oneorganofunctional silane compound; and, optionally, b) one organic acid,and/or one silicon-free precursor compound comprising an organic acid,or the masterkit of claim 9, in a sioplas process, or 6) reacting thedifferent mixture with a composition comprising: a) at least onesilicon-comprising precursor compound of an organic acid, and/or oneorganofunctional silane compound; and, optionally, b) one organic acid,and/or one silicon-free precursor compound comprising an organic acid,or the masterkit of claim 9, in a copolymerization process.
 12. Theprocess of claim 1, wherein at least one silane-grafted orsilane-copolymerized, and/or filled or unfilled compounded polymermaterial, and/or crosslinked, filled, or crosslinked, unfilled polymeris produced.
 13. A polymer, a compounded polymer material, or anunfilled or filled plastic, obtained by the process of claim
 10. 14. Amolding, obtained by the process of claim
 10. 15. A polymer kit,comprising: a composition comprising: a) at least one silicon-comprisingprecursor compound of an organic acid, and/or one organofunctionalsilane compound; and, optionally, b) one organic acid, and/or onesilicon-free precursor compound comprising an organic acid, and/or themasterkit of claim 9, and separately therefrom, at least one selectedfrom the group consisting of a thermoplastic parent polymer, asilane-grafted parent polymer, a silane-copolymerized parent polymer, amonomer of the parent polymer, and prepolymer of the parent polymer. 16.(canceled)
 17. The composition of claim 3, wherein the ester is presentand is selected from the group consisting of a natural triglyceride, asynthetic triglyceride, and a phosphoglyceride.
 18. The composition ofclaim 4, wherein the free-radical generator is at least one selectedfrom the group consisting of tert-butyl peroxypivalate, tert-butyl2-ethylperoxyhexanoate, dicumyl peroxide, di-tert-butyl peroxide,tert-butyl cumyl peroxide, 1,3-di(2-tert-butylperoxyisopropyl)benzene,2,5-dimethyl-2,5-bis(tert-butylperoxy)hex-3-yne, di-tert-amyl peroxide,1,3,5-tris(2-tert-butylperoxyisopropyl)benzene,1-phenyl-1-tert-butylperoxyphthalide,alpha,alpha′-bis(tert-butylperoxy)diisopropylbenzene,2,5-dimethyl-2,5-di-tert-butylperoxyhexane,1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, n-butyl4,4-di(tert-butylperoxy)valerate, ethyl(3,3-di(tert-butylperoxy)butyrate, and3,3,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane.
 19. The masterkit ofclaim 10, wherein as component A, the at least one silicon-comprisingprecursor compound has formula I and/or II(A)_(z)SiR² _(x)(OR¹)_(4-z-x)   (I)(R¹O)_(3-y-u)(R²)_(u)(A)_(y)Si-A-Si(A)_(y)(R²)_(u)(OR¹)_(3-y-u)   (II),wherein mutually independently, z is 0, 1, 2, or 3, x is 0, 1, 2, or 3,y is 0, 1, 2, or 3, and u is 0, 1, 2, or 3, with the proviso that, informula I, z+x is smaller than or equal to (≦)3, and, in formula II, y+uis independently smaller than or equal to (≦)2, A is mutuallyindependently in formula I and/or II a monovalent olefin group, and A inthe form of a divalent moiety in formula II is a divalent olefin group,R¹ is, mutually independently, a carbonyl-R³ group, where R³ correspondsto a hydrocarbon moiety, having from 1 to 45 carbon atoms, and R²corresponds, mutually independently, to a hydrocarbon group.
 20. Thecomposition of claim 3, further comprising: c), at least onefree-radical generator.
 21. The composition of claim 3, furthercomprising: d), at least one selected from the group consisting of astabilizer and a further added substance.